Extended BODIPYs as Red–NIR Laser Radiation Sources with Emission from 610 nm to 750 nm

Ci a ion: Oliden-Sánchez, A.;
Al a ado-Ma ínez, E.;
Ramí ez-O nelas, D.E.; Vázquez,
M.A.; A ellanal-Zaballa, E.; Bañuelos,
J.; Peña-Cab e a, E. Ex ended
BODIPYs as Red–NIR Lase
Radia ion Sou ces wi h Emission
om 610 nm o 750 nm. Molecules
2023,28, 4750. h ps://doi.o g/
10.3390/molecules28124750
Academic Edi o : Lucia Panzella
Recei ed: 18 May 2023
Re ised: 11 June 2023
Accep ed: 12 June 2023
Published: 13 June 2023
Copy igh : © 2023 by he au ho s.
Licensee MDPI, Basel, Swi ze land.
This a icle is an open access a icle
dis ibu ed unde he e ms and
condi ions o he C ea i e Commons
A ibu ion (CC BY) license (h ps://
c ea i ecommons.o g/licenses/by/
4.0/).
molecules
A icle
Ex ended BODIPYs as Red–NIR Lase Radia ion Sou ces wi h
Emission om 610 nm o 750 nm
Ainhoa Oliden-Sánchez 1, En ique Al a ado-Ma ínez 2, Diana E. Ramí ez-O nelas 2, Miguel A. Vázquez 2,
Edu ne A ellanal-Zaballa 1, Jo ge Bañuelos 1,* and Edua do Peña-Cab e a 2,*
1
Depa amen o de Química Física, Uni e sidad del País Vasco (UPV/EHU), Ba io Sa iena s/n, Ap ado 644,
48940 Leioa, Bizkaia, Spain; [email p o ec ed] (A.O.-S.); [email p o ec ed] (E.A.-Z.)
2Depa amen o de Química, Uni e sidad de Guanajua o, No ia Al a s/n, Guanajua o 36050,
Guanajua o, Mexico; [email p o ec ed] (E.A.-M.); [email p o ec ed] (D.E.R.-O.);
[email p o ec ed] (M.A.V.)
*Co espondence: [email p o ec ed] (J.B.); edua [email p o ec ed] (E.P.-C.)
Abs ac :
He ein, we epo he syn he ic access o a se o
π
-ex ended BODIPYs ea u ing a pen a-
a yla ed (phenyl and/o hiophene) dipy in amewo k. We ake ad an age o he ull chemose-
lec i e con ol o 8-me hyl hio-2,3,5,6- e ab omoBODIPY when we conduc he Liebeskind–S ogl
c oss-coupling (LSCC) o unc ionalize exclusi ely he meso-posi ion, ollowed by he e a-Suzuki
eac ion o a yla e he halogena ed si es. All hese lase dyes display abso p ion and emission bands
in he ed edge o he isible spec um eaching he nea -in a ed wi h hiophene unc ionaliza ion.
The emission e iciency, bo h luo escence and lase , o he polyphenylBODIPYs can be enhanced
upon deco a ion o he pe iphe al phenyls wi h elec on dono /accep o g oups a pa a posi ions.
Al e na i ely, he poly hiopheneBODIPYs show an as onishing lase pe o mance despi e he cha ge
ans e cha ac e o he emi ing s a e. The e o e, hese BODIPYs a e sui able as a pale e o s able
and b igh lase sou ces co e ing he spec al egion om 610 nm o 750 nm.
Keywo ds: BODIPY; cha ge ans e ; dyes/pigmen s; luo escence; lase spec oscopy
1. In oduc ion
The ques o no el a - ed and nea -in a ed (NIR) luo opho es is an eme ging ield
in dye chemis y [
1
–
3
]. Nowadays, luo escen imaging has become a powe ul ool o
isualize biological sys ems and ack biomolecules unde ad anced luo escen mic o-
scopes wi h supe esolu ion (single molecule) [
4
–
6
]. This echnique demands molecula
p obes wo king in he so-called biological o he apeu ic window (beyond 650 nm), owing
o he deep- issue pene a ion o his long-wa eleng h adia ion (2–5 cm) [
7
–
10
]. These
luo opho es should be chemically obus and pho os able in o de o display long las ing
luo escen images, and eadily a ailable o pos - unc ionaliza ion o allow a ge able la-
belling [
11
]. Ano he aspec o hese ed–NIR luminopho es is he de elopmen o low-cos
exci a ion sou ces in op ical ibe s applied in elecommunica ions ( elecom ange beyond
800 nm) owing o he lowe in e e ence and sca e ing o his long-wa eleng h adia ion
wi h i s su oundings, allowing he ligh o a el longe dis ances [12,13].
Among he a ious classes o o ganic dyes es ed as ligh emission sou ces in his
sough a e spec al window (mainly based on cyanine, po phy in and ph alocyanine skele-
ons) [
14
,
15
], BODIPY de i a i es a e in he spo ligh [
16
,
17
]. This mode n luo opho e, a
s uc u al analogue o po phy in, enables applica ion o se e al syn he ic s a egies o push
he abso p ion and emission owa ds longe wa eleng hs while e aining hei excellen
pho ophysical signa u es [
18
–
20
]. Acco ding o he li e a u e, se e al app oaches ha e
been success ully es ed o span he delocalized
π
-sys em o he dipy in co e and each
he ed–NIR spec al window. The main s a egies in ol e he usion o a oma ic ings
(a yls and he e ocycles, and e en o he BODIPYs) [
21
–
23
], pe iphe al linkage o a oma ic
Molecules 2023,28, 4750. h ps://doi.o g/10.3390/molecules28124750 h ps://www.mdpi.com/jou nal/molecules
Molecules 2023,28, 4750 2 o 15
amewo ks ( o ins ance, s y yls and he a o emen ioned cyclic moie ies) [
24
–
26
], eplace-
men o he meso-ca bon by ni ogen (aza-BODIPYs) [
27
,
28
], g a ing elec on eleasing and
wi hd awing unc ionaliza ions (push-pull BODIPYs) [
29
,
30
], and he combina ion o some
o hese molecula s a egies in o a single s uc u e [
31
]. F om such su eys, we ind ha
he e he ing o a oma ic amewo ks, p ope ly unc ionalized wi h elec on ich g oups,
a he py olic
β
and
α
posi ions, is one o he success ul s a egies o induce p onounced
spec al shi s, while e aining he high abso p ion and emission e iciency cha ac e is ics
o his amily o dyes. Mo eo e , i would be highly ad an ageous o ha e ull con ol o
he unc ionaliza ion o he di e en BODIPY posi ions o be able o ailo he physical (e.g.,
solubili y) and pho ophysical p ope ies o he inal p oduc s.
In espec o his backg ound, we syn hesized wo se s o 8-a ylBODIPY-based lu-
o opho es (Scheme 1). On he one hand, we syn hesized polya yla ed BODIPYs bea ing
2,3,5,6-phenyls pa a- unc ionalized wi h elec on wi hd awing ( o myl, i luo ome hyl
and cyano) and elec on neu al o dono g oups ( ime hylsilyl and me hoxy). On he
o he hand, we syn hesized poly hiopheneBODIPYs bea ing such sul u -con aining he e-
ocycles a he same abo e-men ioned posi ions. To asce ain he ole o he 8-a yl g oup,
i s s e eoelec onic p ope ies we e sys ema ically a ied, adding s e ic cons ain s ia
o ho-me hyla ion o g a ing elec on dono (me hoxy) o accep o ( o myl) g oups a i s
pa a posi ion. The main aim o hese long-wa eleng h emi ing
π
-ex ended BODIPYs is
o deciphe he s uc u al ac o s ha igge he spec al shi and he emission e iciency
(bo h luo escence and lase ) and p o ide a cha o luo opho es ha a e e icien and
s able a - ed–NIR lase sou ces. Acco dingly, we ha e e alua ed hei pho onic signa u es
unde so (pho ophysical p ope ies) and ha d (lase pe o mance) i adia ion egimes and
a ionalized hem assis ed by compu a ional simula ions.
Molecules 2023, 28, x FOR PEER REVIEW 2 o 15
se e al app oaches ha e been success ully es ed o span he delocalized π-sys em o he
dipy in co e and each he ed–NIR spec al window. The main s a egies in ol e he
usion o a oma ic ings (a yls and he e ocycles, and e en o he BODIPYs) [21–23],
pe iphe al linkage o a oma ic amewo ks ( o ins ance, s y yls and he a o emen ioned
cyclic moie ies) [24–26], eplacemen o he meso-ca bon by ni ogen (aza-BODIPYs)
[27,28], g a ing elec on eleasing and wi hd awing unc ionaliza ions (push-pull
BODIPYs) [29,30], and he combina ion o some o hese molecula s a egies in o a single
s uc u e [31]. F om such su eys, we ind ha he e he ing o a oma ic amewo ks,
p ope ly unc ionalized wi h elec on ich g oups, a he py olic β and α posi ions, is one
o he success ul s a egies o induce p onounced spec al shi s, while e aining he high
abso p ion and emission e iciency cha ac e is ics o his amily o dyes. Mo eo e , i
would be highly ad an ageous o ha e ull con ol o he unc ionaliza ion o he di e en
BODIPY posi ions o be able o ailo he physical (e.g., solubili y) and pho ophysical
p ope ies o he inal p oduc s.
In espec o his backg ound, we syn hesized wo se s o 8-a ylBODIPY-based
luo opho es (Scheme 1). On he one hand, we syn hesized polya yla ed BODIPYs bea ing
2,3,5,6-phenyls pa a- unc ionalized wi h elec on wi hd awing ( o myl, i luo ome hyl
and cyano) and elec on neu al o dono g oups ( ime hylsilyl and me hoxy). On he
o he hand, we syn hesized poly hiopheneBODIPYs bea ing such sul u -con aining
he e ocycles a he same abo e-men ioned posi ions. To asce ain he ole o he 8-a yl
g oup, i s s e eoelec onic p ope ies we e sys ema ically a ied, adding s e ic cons ain s
ia o ho-me hyla ion o g a ing elec on dono (me hoxy) o accep o ( o myl) g oups a
i s pa a posi ion. The main aim o hese long-wa eleng h emi ing π-ex ended BODIPYs
is o deciphe he s uc u al ac o s ha igge he spec al shi and he emission
e iciency (bo h luo escence and lase ) and p o ide a cha o luo opho es ha a e
e icien and s able a - ed–NIR lase sou ces. Acco dingly, we ha e e alua ed hei
pho onic signa u es unde so (pho ophysical p ope ies) and ha d (lase pe o mance)
i adia ion egimes and a ionalized hem assis ed by compu a ional simula ions.
Scheme 1. Molecula s uc u e o he ed–NIR emi ing BODIPYs.
2. Resul s and Discussion
2.1. Syn hesis
Recen ly, we epo ed he syn hesis o no el BODIPY building block 2 h ough a
e ab omina ion eac ion o comme cially a ailable 8-me hyl hioBODIPY 1 and
demons a ed ha i displayed o hogonal eac i i y [32]. The C–S bond was ac i a ed
unde Liebeskind–S ogl c oss-coupling eac ion (LSCC) condi ions, lea ing he C–B
bonds in ac [33]. This esul allowed he selec i e unc ionaliza ion o he meso-posi ion
lea ing he o he b omina ed posi ions a ailable o be manipula ed a will. In his con ex ,
Scheme 1. Molecula s uc u e o he ed–NIR emi ing BODIPYs.
2. Resul s and Discussion
2.1. Syn hesis
Recen ly, we epo ed he syn hesis o no el BODIPY building block
2
h ough a
e ab omina ion eac ion o comme cially a ailable 8-me hyl hioBODIPY
1
and demon-
s a ed ha i displayed o hogonal eac i i y [
32
]. The C–S bond was ac i a ed unde
Liebeskind–S ogl c oss-coupling eac ion (LSCC) condi ions, lea ing he C–B bonds in-
ac [
33
]. This esul allowed he selec i e unc ionaliza ion o he meso-posi ion lea ing he
o he b omina ed posi ions a ailable o be manipula ed a will. In his con ex , we decided
o e alua e a quad uple Suzuki–Miyau a c oss-coupling eac ion o ob ain a new amily o
poly (he )a ylBODIPY dyes (Scheme 2).
Molecules 2023,28, 4750 3 o 15
Molecules 2023, 28, x FOR PEER REVIEW 3 o 15
we decided o e alua e a quad uple Suzuki–Miyau a c oss-coupling eac ion o ob ain a
new amily o poly (he )a ylBODIPY dyes (Scheme 2).
Scheme 2. Re osyn he ic analysis o he syn hesis o poly-(he )a ylBODIPYs.
We ini ially syn hesized BODIPY 2 acco ding o Scheme 3.
Scheme 3. Syn hesis o he e ab omina ed 8-me hyl hioBODIPY p ecu so 2.
Wi h 2 in hand, a chemoselec i e LSCC eac ion was ca ied ou o access
e ab omina ed meso-a ylBODIPYs 3 acco ding o Scheme 4. Se e al a ylbo onic acids
we e e alua ed, accessing i e de i a i es in modes o good yields (18–76%) in sho
eac ion imes.
Scheme 4. Syn hesis o e ab omina ed meso-a ylBODIPYs ia LSCC eac ion, s uc u e o he ed–
NIR emi ing BODIPYs. Condi ions: BODIPY 2 (1 equi .), bo onic acid (3 equi .), Pd2(dba)3 (2.5
mol%), TFP (7.5 mol%), CuTC (3 equi .) in THF (0.03 M) a 55 °C.
Scheme 2. Re osyn he ic analysis o he syn hesis o poly-(he )a ylBODIPYs.
We ini ially syn hesized BODIPY 2acco ding o Scheme 3.
Molecules 2023, 28, x FOR PEER REVIEW 3 o 15
we decided o e alua e a quad uple Suzuki–Miyau a c oss-coupling eac ion o ob ain a
new amily o poly (he )a ylBODIPY dyes (Scheme 2).
Scheme 2. Re osyn he ic analysis o he syn hesis o poly-(he )a ylBODIPYs.
We ini ially syn hesized BODIPY 2 acco ding o Scheme 3.
Scheme 3. Syn hesis o he e ab omina ed 8-me hyl hioBODIPY p ecu so 2.
Wi h 2 in hand, a chemoselec i e LSCC eac ion was ca ied ou o access
e ab omina ed meso-a ylBODIPYs 3 acco ding o Scheme 4. Se e al a ylbo onic acids
we e e alua ed, accessing i e de i a i es in modes o good yields (18–76%) in sho
eac ion imes.
Scheme 4. Syn hesis o e ab omina ed meso-a ylBODIPYs ia LSCC eac ion, s uc u e o he ed–
NIR emi ing BODIPYs. Condi ions: BODIPY 2 (1 equi .), bo onic acid (3 equi .), Pd2(dba)3 (2.5
mol%), TFP (7.5 mol%), CuTC (3 equi .) in THF (0.03 M) a 55 °C.
Scheme 3. Syn hesis o he e ab omina ed 8-me hyl hioBODIPY p ecu so 2.
Wi h
2
in hand, a chemoselec i e LSCC eac ion was ca ied ou o access e ab omi-
na ed meso-a ylBODIPYs
3
acco ding o Scheme 4. Se e al a ylbo onic acids we e e alua ed,
accessing i e de i a i es in modes o good yields (18–76%) in sho eac ion imes.
Molecules 2023, 28, x FOR PEER REVIEW 3 o 15
we decided o e alua e a quad uple Suzuki–Miyau a c oss-coupling eac ion o ob ain a
new amily o poly (he )a ylBODIPY dyes (Scheme 2).
Scheme 2. Re osyn he ic analysis o he syn hesis o poly-(he )a ylBODIPYs.
We ini ially syn hesized BODIPY 2 acco ding o Scheme 3.
Scheme 3. Syn hesis o he e ab omina ed 8-me hyl hioBODIPY p ecu so 2.
Wi h 2 in hand, a chemoselec i e LSCC eac ion was ca ied ou o access
e ab omina ed meso-a ylBODIPYs 3 acco ding o Scheme 4. Se e al a ylbo onic acids
we e e alua ed, accessing i e de i a i es in modes o good yields (18–76%) in sho
eac ion imes.
Scheme 4. Syn hesis o e ab omina ed meso-a ylBODIPYs ia LSCC eac ion, s uc u e o he ed–
NIR emi ing BODIPYs. Condi ions: BODIPY 2 (1 equi .), bo onic acid (3 equi .), Pd2(dba)3 (2.5
mol%), TFP (7.5 mol%), CuTC (3 equi .) in THF (0.03 M) a 55 °C.
Scheme 4.
Syn hesis o e ab omina ed meso-a ylBODIPYs ia LSCC eac ion, s uc u e o he
ed–NIR emi ing BODIPYs. Condi ions: BODIPY
2
(1 equi .), bo onic acid (3 equi .), Pd
2
(dba)
3
(2.5 mol%), TFP (7.5 mol%), CuTC (3 equi .) in THF (0.03 M) a 55 ◦C.
Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ion-
aliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in
3a
(Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o
he mul iple unc ionaliza ion o BODIPYs [
34
,
35
]. Fo en y 1, he eac ion was incomple e,
Molecules 2023,28, 4750 4 o 15
and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc
4
was isola ed
in 42% yield. When we used Pd(OAc)
2
and SPhos, along wi h K
3
PO
4
as a base, he yield o
4 inc eased o 52% (en y 3 in Table S1).
Once he bes condi ions we e de e mined, we se ou o eac
3a
–
e
wi h se e al
(he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he
Suzuki–Miyau a
c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o
3a
–
e
a e
shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly
and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely
sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies
1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in
yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he
eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion
imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl
subs i uen s we e modi ied.
Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e1.
Molecules 2023, 28, x FOR PEER REVIEW 4 o 15
Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple
unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling
eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in
he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he
eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he
desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along
wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1).
Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al
(he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki–
Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion
o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook
place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o
83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he
highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically,
he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2-
hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic
acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was
obse ed when he meso-a yl subs i uen s we e modi ied.
Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1.
En y A R-B(OH)2
Reac ion
Time
Yield
2
(%)
Compound
1
S
20 min 80 4a
2
S
20 min 83 4b
3
S
20 min 65 4c
4
MeO
S
25 min 76 4d
5
OHC
S
2 h 55 4e
6
4 h
52
4
7
4 h 57 4g
8
F
3
C
5 h
41
4h
9
MeO
2 h 65 4i
10
MeOC
14 h 65 4j
11
MeO
Me
3
Si
4 h 63 4k
12
MeO
NC
16 h
57
4l
1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16
equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield.
2.2. Pho ophysical P ope ies
The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em
pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission
o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl
does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed
geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound
En y A R-B(OH)2Reac ion
Time
Yield 2
(%) Compound
1
Molecules 2023, 28, x FOR PEER REVIEW 4 o 15
Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple
unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling
eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in
he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he
eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he
desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along
wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1).
Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al
(he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki–
Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion
o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook
place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o
83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he
highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically,
he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2-
hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic
acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was
obse ed when he meso-a yl subs i uen s we e modi ied.
Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1.
En y A R-B(OH)2
Reac ion
Time
Yield
2
(%)
Compound
1
S
20 min 80 4a
2
S
20 min 83 4b
3
S
20 min 65 4c
4
MeO
S
25 min 76 4d
5
OHC
S
2 h 55 4e
6
4 h
52
4
7
4 h 57 4g
8
F
3
C
5 h
41
4h
9
MeO
2 h 65 4i
10
MeOC
14 h 65 4j
11
MeO
Me
3
Si
4 h 63 4k
12
MeO
NC
16 h
57
4l
1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16
equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield.
2.2. Pho ophysical P ope ies
The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em
pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission
o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl
does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed
geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound
Molecules 2023, 28, x FOR PEER REVIEW 4 o 15
Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple
unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling
eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in
he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he
eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he
desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along
wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1).
Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al
(he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki–
Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion
o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook
place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o
83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he
highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically,
he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2-
hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic
acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was
obse ed when he meso-a yl subs i uen s we e modi ied.
Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1.
En y A R-B(OH)2
Reac ion
Time
Yield
2
(%)
Compound
1
S
20 min 80 4a
2
S
20 min 83 4b
3
S
20 min 65 4c
4
MeO
S
25 min 76 4d
5
OHC
S
2 h 55 4e
6
4 h
52
4
7
4 h 57 4g
8
F
3
C
5 h
41
4h
9
MeO
2 h 65 4i
10
MeOC
14 h 65 4j
11
MeO
Me
3
Si
4 h 63 4k
12
MeO
NC
16 h
57
4l
1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16
equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield.
2.2. Pho ophysical P ope ies
The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em
pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission
o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl
does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed
geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound
20 min 80 4a
2
Molecules 2023, 28, x FOR PEER REVIEW 4 o 15
Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple
unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling
eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in
he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he
eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he
desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along
wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1).
Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al
(he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki–
Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion
o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook
place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o
83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he
highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically,
he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2-
hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic
acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was
obse ed when he meso-a yl subs i uen s we e modi ied.
Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1.
En y A R-B(OH)2
Reac ion
Time
Yield
2
(%)
Compound
1
S
20 min 80 4a
2
S
20 min 83 4b
3
S
20 min 65 4c
4
MeO
S
25 min 76 4d
5
OHC
S
2 h 55 4e
6
4 h
52
4
7
4 h 57 4g
8
F
3
C
5 h
41
4h
9
MeO
2 h 65 4i
10
MeOC
14 h 65 4j
11
MeO
Me
3
Si
4 h 63 4k
12
MeO
NC
16 h
57
4l
1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16
equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield.
2.2. Pho ophysical P ope ies
The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em
pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission
o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl
does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed
geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound
Molecules 2023, 28, x FOR PEER REVIEW 4 o 15
Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple
unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling
eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in
he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he
eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he
desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along
wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1).
Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al
(he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki–
Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion
o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook
place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o
83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he
highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically,
he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2-
hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic
acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was
obse ed when he meso-a yl subs i uen s we e modi ied.
Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1.
En y A R-B(OH)2
Reac ion
Time
Yield
2
(%)
Compound
1
S
20 min 80 4a
2
S
20 min 83 4b
3
S
20 min 65 4c
4
MeO
S
25 min 76 4d
5
OHC
S
2 h 55 4e
6
4 h
52
4
7
4 h 57 4g
8
F
3
C
5 h
41
4h
9
MeO
2 h 65 4i
10
MeOC
14 h 65 4j
11
MeO
Me
3
Si
4 h 63 4k
12
MeO
NC
16 h
57
4l
1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16
equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield.
2.2. Pho ophysical P ope ies
The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em
pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission
o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl
does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed
geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound
20 min 83 4b
3
Molecules 2023, 28, x FOR PEER REVIEW 4 o 15
Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple
unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling
eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in
he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he
eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he
desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along
wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1).
Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al
(he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki–
Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion
o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook
place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o
83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he
highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically,
he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2-
hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic
acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was
obse ed when he meso-a yl subs i uen s we e modi ied.
Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1.
En y A R-B(OH)2
Reac ion
Time
Yield
2
(%)
Compound
1
S
20 min 80 4a
2
S
20 min 83 4b
3
S
20 min 65 4c
4
MeO
S
25 min 76 4d
5
OHC
S
2 h 55 4e
6
4 h
52
4
7
4 h 57 4g
8
F
3
C
5 h
41
4h
9
MeO
2 h 65 4i
10
MeOC
14 h 65 4j
11
MeO
Me
3
Si
4 h 63 4k
12
MeO
NC
16 h
57
4l
1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16
equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield.
2.2. Pho ophysical P ope ies
The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em
pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission
o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl
does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed
geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound
Molecules 2023, 28, x FOR PEER REVIEW 4 o 15
Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple
unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling
eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in
he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he
eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he
desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along
wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1).
Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al
(he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki–
Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion
o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook
place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o
83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he
highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically,
he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2-
hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic
acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was
obse ed when he meso-a yl subs i uen s we e modi ied.
Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1.
En y A R-B(OH)2
Reac ion
Time
Yield
2
(%)
Compound
1
S
20 min 80 4a
2
S
20 min 83 4b
3
S
20 min 65 4c
4
MeO
S
25 min 76 4d
5
OHC
S
2 h 55 4e
6
4 h
52
4
7
4 h 57 4g
8
F
3
C
5 h
41
4h
9
MeO
2 h 65 4i
10
MeOC
14 h 65 4j
11
MeO
Me
3
Si
4 h 63 4k
12
MeO
NC
16 h
57
4l
1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16
equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield.
2.2. Pho ophysical P ope ies
The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em
pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission
o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl
does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed
geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound
20 min 65 4c
4
Molecules 2023, 28, x FOR PEER REVIEW 4 o 15
Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple
unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling
eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in
he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he
eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he
desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along
wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1).
Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al
(he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki–
Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion
o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook
place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o
83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he
highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically,
he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2-
hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic
acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was
obse ed when he meso-a yl subs i uen s we e modi ied.
Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1.
En y A R-B(OH)2
Reac ion
Time
Yield
2
(%)
Compound
1
S
20 min 80 4a
2
S
20 min 83 4b
3
S
20 min 65 4c
4
MeO
S
25 min 76 4d
5
OHC
S
2 h 55 4e
6
4 h
52
4
7
4 h 57 4g
8
F
3
C
5 h
41
4h
9
MeO
2 h 65 4i
10
MeOC
14 h 65 4j
11
MeO
Me
3
Si
4 h 63 4k
12
MeO
NC
16 h
57
4l
1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16
equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield.
2.2. Pho ophysical P ope ies
The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em
pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission
o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl
does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed
geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound
Molecules 2023, 28, x FOR PEER REVIEW 4 o 15
Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple
unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling
eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in
he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he
eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he
desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along
wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1).
Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al
(he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki–
Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion
o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook
place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o
83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he
highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically,
he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2-
hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic
acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was
obse ed when he meso-a yl subs i uen s we e modi ied.
Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1.
En y A R-B(OH)2
Reac ion
Time
Yield
2
(%)
Compound
1
S
20 min 80 4a
2
S
20 min 83 4b
3
S
20 min 65 4c
4
MeO
S
25 min 76 4d
5
OHC
S
2 h 55 4e
6
4 h
52
4
7
4 h 57 4g
8
F
3
C
5 h
41
4h
9
MeO
2 h 65 4i
10
MeOC
14 h 65 4j
11
MeO
Me
3
Si
4 h 63 4k
12
MeO
NC
16 h
57
4l
1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16
equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield.
2.2. Pho ophysical P ope ies
The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em
pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission
o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl
does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed
geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound
25 min 76 4d
5
Molecules 2023, 28, x FOR PEER REVIEW 4 o 15
Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple
unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling
eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in
he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he
eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he
desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along
wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1).
Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al
(he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki–
Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion
o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook
place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o
83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he
highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically,
he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2-
hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic
acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was
obse ed when he meso-a yl subs i uen s we e modi ied.
Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1.
En y A R-B(OH)2
Reac ion
Time
Yield
2
(%)
Compound
1
S
20 min 80 4a
2
S
20 min 83 4b
3
S
20 min 65 4c
4
MeO
S
25 min 76 4d
5
OHC
S
2 h 55 4e
6
4 h
52
4
7
4 h 57 4g
8
F
3
C
5 h
41
4h
9
MeO
2 h 65 4i
10
MeOC
14 h 65 4j
11
MeO
Me
3
Si
4 h 63 4k
12
MeO
NC
16 h
57
4l
1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16
equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield.
2.2. Pho ophysical P ope ies
The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em
pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission
o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl
does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed
geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound
Molecules 2023, 28, x FOR PEER REVIEW 4 o 15
Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple
unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling
eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in
he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he
eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he
desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along
wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1).
Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al
(he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki–
Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion
o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook
place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o
83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he
highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically,
he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2-
hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic
acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was
obse ed when he meso-a yl subs i uen s we e modi ied.
Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1.
En y A R-B(OH)2
Reac ion
Time
Yield
2
(%)
Compound
1
S
20 min 80 4a
2
S
20 min 83 4b
3
S
20 min 65 4c
4
MeO
S
25 min 76 4d
5
OHC
S
2 h 55 4e
6
4 h
52
4
7
4 h 57 4g
8
F
3
C
5 h
41
4h
9
MeO
2 h 65 4i
10
MeOC
14 h 65 4j
11
MeO
Me
3
Si
4 h 63 4k
12
MeO
NC
16 h
57
4l
1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16
equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield.
2.2. Pho ophysical P ope ies
The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em
pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission
o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl
does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed
geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound
2 h 55 4e
6
Molecules 2023, 28, x FOR PEER REVIEW 4 o 15
Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple
unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling
eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in
he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he
eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he
desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along
wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1).
Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al
(he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki–
Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion
o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook
place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o
83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he
highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically,
he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2-
hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic
acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was
obse ed when he meso-a yl subs i uen s we e modi ied.
Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1.
En y A R-B(OH)2
Reac ion
Time
Yield
2
(%)
Compound
1
S
20 min 80 4a
2
S
20 min 83 4b
3
S
20 min 65 4c
4
MeO
S
25 min 76 4d
5
OHC
S
2 h 55 4e
6
4 h
52
4
7
4 h 57 4g
8
F
3
C
5 h
41
4h
9
MeO
2 h 65 4i
10
MeOC
14 h 65 4j
11
MeO
Me
3
Si
4 h 63 4k
12
MeO
NC
16 h
57
4l
1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16
equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield.
2.2. Pho ophysical P ope ies
The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em
pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission
o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl
does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed
geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound
Molecules 2023, 28, x FOR PEER REVIEW 4 o 15
Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple
unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling
eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in
he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he
eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he
desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along
wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1).
Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al
(he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki–
Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion
o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook
place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o
83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he
highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically,
he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2-
hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic
acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was
obse ed when he meso-a yl subs i uen s we e modi ied.
Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1.
En y A R-B(OH)2
Reac ion
Time
Yield
2
(%)
Compound
1
S
20 min 80 4a
2
S
20 min 83 4b
3
S
20 min 65 4c
4
MeO
S
25 min 76 4d
5
OHC
S
2 h 55 4e
6
4 h
52
4
7
4 h 57 4g
8
F
3
C
5 h
41
4h
9
MeO
2 h 65 4i
10
MeOC
14 h 65 4j
11
MeO
Me
3
Si
4 h 63 4k
12
MeO
NC
16 h
57
4l
1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16
equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield.
2.2. Pho ophysical P ope ies
The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em
pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission
o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl
does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed
geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound
4 h 52 4
7
Molecules 2023, 28, x FOR PEER REVIEW 4 o 15
Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple
unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling
eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in
he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he
eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he
desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along
wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1).
Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al
(he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki–
Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion
o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook
place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o
83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he
highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically,
he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2-
hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic
acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was
obse ed when he meso-a yl subs i uen s we e modi ied.
Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1.
En y A R-B(OH)2
Reac ion
Time
Yield
2
(%)
Compound
1
S
20 min 80 4a
2
S
20 min 83 4b
3
S
20 min 65 4c
4
MeO
S
25 min 76 4d
5
OHC
S
2 h 55 4e
6
4 h
52
4
7
4 h 57 4g
8
F
3
C
5 h
41
4h
9
MeO
2 h 65 4i
10
MeOC
14 h 65 4j
11
MeO
Me
3
Si
4 h 63 4k
12
MeO
NC
16 h
57
4l
1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16
equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield.
2.2. Pho ophysical P ope ies
The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em
pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission
o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl
does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed
geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound
Molecules 2023, 28, x FOR PEER REVIEW 4 o 15
Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple
unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling
eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in
he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he
eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he
desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along
wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1).
Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al
(he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki–
Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion
o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook
place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o
83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he
highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically,
he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2-
hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic
acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was
obse ed when he meso-a yl subs i uen s we e modi ied.
Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1.
En y A R-B(OH)2
Reac ion
Time
Yield
2
(%)
Compound
1
S
20 min 80 4a
2
S
20 min 83 4b
3
S
20 min 65 4c
4
MeO
S
25 min 76 4d
5
OHC
S
2 h 55 4e
6
4 h
52
4
7
4 h 57 4g
8
F
3
C
5 h
41
4h
9
MeO
2 h 65 4i
10
MeOC
14 h 65 4j
11
MeO
Me
3
Si
4 h 63 4k
12
MeO
NC
16 h
57
4l
1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16
equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield.
2.2. Pho ophysical P ope ies
The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em
pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission
o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl
does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed
geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound
4 h 57 4g
8
Molecules 2023, 28, x FOR PEER REVIEW 4 o 15
Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple
unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling
eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in
he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he
eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he
desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along
wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1).
Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al
(he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki–
Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion
o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook
place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o
83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he
highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically,
he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2-
hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic
acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was
obse ed when he meso-a yl subs i uen s we e modi ied.
Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1.
En y A R-B(OH)2
Reac ion
Time
Yield
2
(%)
Compound
1
S
20 min 80 4a
2
S
20 min 83 4b
3
S
20 min 65 4c
4
MeO
S
25 min 76 4d
5
OHC
S
2 h 55 4e
6
4 h
52
4
7
4 h 57 4g
8
F
3
C
5 h
41
4h
9
MeO
2 h 65 4i
10
MeOC
14 h 65 4j
11
MeO
Me
3
Si
4 h 63 4k
12
MeO
NC
16 h
57
4l
1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16
equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield.
2.2. Pho ophysical P ope ies
The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em
pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission
o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl
does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed
geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound
Molecules 2023, 28, x FOR PEER REVIEW 4 o 15
Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple
unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling
eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in
he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he
eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he
desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along
wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1).
Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al
(he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki–
Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion
o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook
place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o
83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he
highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically,
he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2-
hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic
acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was
obse ed when he meso-a yl subs i uen s we e modi ied.
Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1.
En y A R-B(OH)2
Reac ion
Time
Yield
2
(%)
Compound
1
S
20 min 80 4a
2
S
20 min 83 4b
3
S
20 min 65 4c
4
MeO
S
25 min 76 4d
5
OHC
S
2 h 55 4e
6
4 h
52
4
7
4 h 57 4g
8
F
3
C
5 h
41
4h
9
MeO
2 h 65 4i
10
MeOC
14 h 65 4j
11
MeO
Me
3
Si
4 h 63 4k
12
MeO
NC
16 h
57
4l
1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16
equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield.
2.2. Pho ophysical P ope ies
The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em
pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission
o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl
does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed
geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound
5 h 41 4h
9
Molecules 2023, 28, x FOR PEER REVIEW 4 o 15
Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple
unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling
eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in
he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he
eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he
desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along
wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1).
Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al
(he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki–
Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion
o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook
place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o
83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he
highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically,
he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2-
hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic
acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was
obse ed when he meso-a yl subs i uen s we e modi ied.
Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1.
En y A R-B(OH)2
Reac ion
Time
Yield
2
(%)
Compound
1
S
20 min 80 4a
2
S
20 min 83 4b
3
S
20 min 65 4c
4
MeO
S
25 min 76 4d
5
OHC
S
2 h 55 4e
6
4 h
52
4
7
4 h 57 4g
8
F
3
C
5 h
41
4h
9
MeO
2 h 65 4i
10
MeOC
14 h 65 4j
11
MeO
Me
3
Si
4 h 63 4k
12
MeO
NC
16 h
57
4l
1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16
equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield.
2.2. Pho ophysical P ope ies
The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em
pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission
o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl
does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed
geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound
Molecules 2023, 28, x FOR PEER REVIEW 4 o 15
Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple
unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling
eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in
he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he
eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he
desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along
wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1).
Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al
(he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki–
Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion
o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook
place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o
83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he
highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically,
he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2-
hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic
acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was
obse ed when he meso-a yl subs i uen s we e modi ied.
Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1.
En y A R-B(OH)2
Reac ion
Time
Yield
2
(%)
Compound
1
S
20 min 80 4a
2
S
20 min 83 4b
3
S
20 min 65 4c
4
MeO
S
25 min 76 4d
5
OHC
S
2 h 55 4e
6
4 h
52
4
7
4 h 57 4g
8
F
3
C
5 h
41
4h
9
MeO
2 h 65 4i
10
MeOC
14 h 65 4j
11
MeO
Me
3
Si
4 h 63 4k
12
MeO
NC
16 h
57
4l
1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16
equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield.
2.2. Pho ophysical P ope ies
The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em
pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission
o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl
does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed
geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound
2 h 65 4i
10
Molecules 2023, 28, x FOR PEER REVIEW 4 o 15
Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple
unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling
eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in
he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he
eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he
desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along
wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1).
Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al
(he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki–
Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion
o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook
place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o
83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he
highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically,
he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2-
hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic
acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was
obse ed when he meso-a yl subs i uen s we e modi ied.
Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1.
En y A R-B(OH)2
Reac ion
Time
Yield
2
(%)
Compound
1
S
20 min 80 4a
2
S
20 min 83 4b
3
S
20 min 65 4c
4
MeO
S
25 min 76 4d
5
OHC
S
2 h 55 4e
6
4 h
52
4
7
4 h 57 4g
8
F
3
C
5 h
41
4h
9
MeO
2 h 65 4i
10
MeOC
14 h 65 4j
11
MeO
Me
3
Si
4 h 63 4k
12
MeO
NC
16 h
57
4l
1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16
equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield.
2.2. Pho ophysical P ope ies
The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em
pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission
o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl
does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed
geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound
Molecules 2023, 28, x FOR PEER REVIEW 4 o 15
Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple
unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling
eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in
he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he
eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he
desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along
wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1).
Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al
(he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki–
Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion
o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook
place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o
83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he
highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically,
he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2-
hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic
acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was
obse ed when he meso-a yl subs i uen s we e modi ied.
Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1.
En y A R-B(OH)2
Reac ion
Time
Yield
2
(%)
Compound
1
S
20 min 80 4a
2
S
20 min 83 4b
3
S
20 min 65 4c
4
MeO
S
25 min 76 4d
5
OHC
S
2 h 55 4e
6
4 h
52
4
7
4 h 57 4g
8
F
3
C
5 h
41
4h
9
MeO
2 h 65 4i
10
MeOC
14 h 65 4j
11
MeO
Me
3
Si
4 h 63 4k
12
MeO
NC
16 h
57
4l
1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16
equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield.
2.2. Pho ophysical P ope ies
The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em
pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission
o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl
does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed
geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound
14 h 65 4j
11
Molecules 2023, 28, x FOR PEER REVIEW 4 o 15
Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple
unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling
eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in
he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he
eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he
desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along
wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1).
Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al
(he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki–
Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion
o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook
place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o
83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he
highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically,
he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2-
hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic
acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was
obse ed when he meso-a yl subs i uen s we e modi ied.
Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1.
En y A R-B(OH)2
Reac ion
Time
Yield
2
(%)
Compound
1
S
20 min 80 4a
2
S
20 min 83 4b
3
S
20 min 65 4c
4
MeO
S
25 min 76 4d
5
OHC
S
2 h 55 4e
6
4 h
52
4
7
4 h 57 4g
8
F
3
C
5 h
41
4h
9
MeO
2 h 65 4i
10
MeOC
14 h 65 4j
11
MeO
Me
3
Si
4 h 63 4k
12
MeO
NC
16 h
57
4l
1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16
equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield.
2.2. Pho ophysical P ope ies
The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em
pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission
o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl
does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed
geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound
Molecules 2023, 28, x FOR PEER REVIEW 4 o 15
Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple
unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling
eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in
he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he
eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he
desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along
wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1).
Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al
(he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki–
Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion
o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook
place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o
83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he
highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically,
he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2-
hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic
acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was
obse ed when he meso-a yl subs i uen s we e modi ied.
Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1.
En y A R-B(OH)2
Reac ion
Time
Yield
2
(%)
Compound
1
S
20 min 80 4a
2
S
20 min 83 4b
3
S
20 min 65 4c
4
MeO
S
25 min 76 4d
5
OHC
S
2 h 55 4e
6
4 h
52
4
7
4 h 57 4g
8
F
3
C
5 h
41
4h
9
MeO
2 h 65 4i
10
MeOC
14 h 65 4j
11
MeO
Me
3
Si
4 h 63 4k
12
MeO
NC
16 h
57
4l
1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16
equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield.
2.2. Pho ophysical P ope ies
The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em
pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission
o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl
does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed
geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound
4 h 63 4k
12
Molecules 2023, 28, x FOR PEER REVIEW 4 o 15
Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple
unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling
eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in
he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he
eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he
desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along
wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1).
Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al
(he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki–
Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion
o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook
place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o
83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he
highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically,
he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2-
hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic
acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was
obse ed when he meso-a yl subs i uen s we e modi ied.
Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1.
En y A R-B(OH)2
Reac ion
Time
Yield
2
(%)
Compound
1
S
20 min 80 4a
2
S
20 min 83 4b
3
S
20 min 65 4c
4
MeO
S
25 min 76 4d
5
OHC
S
2 h 55 4e
6
4 h
52
4
7
4 h 57 4g
8
F
3
C
5 h
41
4h
9
MeO
2 h 65 4i
10
MeOC
14 h 65 4j
11
MeO
Me
3
Si
4 h 63 4k
12
MeO
NC
16 h
57
4l
1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16
equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield.
2.2. Pho ophysical P ope ies
The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em
pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission
o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl
does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed
geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound
Molecules 2023, 28, x FOR PEER REVIEW 4 o 15
Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple
unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling
eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in
he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he
eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he
desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along
wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1).
Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al
(he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki–
Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion
o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook
place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o
83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he
highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically,
he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2-
hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic
acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was
obse ed when he meso-a yl subs i uen s we e modi ied.
Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1.
En y A R-B(OH)2
Reac ion
Time
Yield
2
(%)
Compound
1
S
20 min 80 4a
2
S
20 min 83 4b
3
S
20 min 65 4c
4
MeO
S
25 min 76 4d
5
OHC
S
2 h 55 4e
6
4 h
52
4
7
4 h 57 4g
8
F
3
C
5 h
41
4h
9
MeO
2 h 65 4i
10
MeOC
14 h 65 4j
11
MeO
Me
3
Si
4 h 63 4k
12
MeO
NC
16 h
57
4l
1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16
equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield.
2.2. Pho ophysical P ope ies
The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em
pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission
o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl
does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed
geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound
16 h 57 4l
1
Condi ions:
3a
(1 equi .), bo onic acid (8 equi .) Pd(OAc)
2
(10 mol%), SPhos (22 mol%), K
3
PO
4
(16 equi .) in
PhCH3a 90 ◦C oo no e. 2Isola ed yield.
2.2. Pho ophysical P ope ies
The a yla ion o he py oles ex ends he ch omopho ic delocalized
π
-sys em pushing
he spec al bands owa ds he ed edge o he isible (abso p ion and emission o
4
and
4g
placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no
Molecules 2023,28, 4750 5 o 15
ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical
a angemen ( heo e ically p edic ed o sion angle a ound 70
◦
om g ound s a e op imized
geome ies) imposed by s e ic easons. The a ained luo escence e iciencies a e lowe
(a ound 30%, Table 2) han hose usually epo ed o g een–yellow emi ing BODIPYs
(usually highe han 80%). This end is ela ed o he ee mo ion o he pe iphe al
phenyls, which enhances he non- adia i e elaxa ion channels ela ed wi h con o ma ional
eedom (no e he unusually high S okes shi , a ound 1000 cm
−1
, sugges ing geome ic
elaxa ion upon exci a ion). Wi h his line o easoning, p e ious publica ions dealing
wi h hep aphenyla ed BODIPYs epo ed simila alues o luo escence e iciencies and
pinpoin ed in e nal con e sion as he main eason [36].
Molecules 2023, 28, x FOR PEER REVIEW 5 o 15
s a e op imized geome ies) imposed by s e ic easons. The a ained luo escence
e iciencies a e lowe (a ound 30%, Table 2) han hose usually epo ed o g een–yellow
emi ing BODIPYs (usually highe han 80%). This end is ela ed o he ee mo ion o
he pe iphe al phenyls, which enhances he non- adia i e elaxa ion channels ela ed wi h
con o ma ional eedom (no e he unusually high S okes shi , a ound 1000 cm−1,
sugges ing geome ic elaxa ion upon exci a ion). Wi h his line o easoning, p e ious
publica ions dealing wi h hep aphenyla ed BODIPYs epo ed simila alues o
luo escence e iciencies and pinpoin ed in e nal con e sion as he main eason [36].
Figu e 1. Rep esen a i e abso p ion (o ange) and luo escence ( ed) spec a o he
polyphenylBODIPY 4 (see Figu e S1 o he spec a o he es o dyes o his amily) in dilu ed
solu ions o cyclohexane. The co esponding con ou maps o he on ie o bi als a e also enclosed.
Table 2. Pho ophysical (2 μM) and lase (0.5–0.75 mM) p ope ies o he polyphenylBODIPYs in
e hyl ace a e. Full pho ophysical and lase da a in mo e media a e lis ed in Tables S2 and S3,
espec i ely.
Dye
λ
ab
1
(nm)
ε
max
∙10
−4
2
(M
−1
∙cm
−1
)
λ
l
3
(nm)
ф 4
τ
5
(ns)
λ
la
6
(nm)
%E 7
E
dose
8
(GJ/mol)
4
577.0
5.0
623.0
0.26
2.28
630.0
8.5
9.0
4g
579.0
5.1
618.0
0.32
2.92
628.0
9.8
9.4
4h
566.5
7.0
597.5
0.47
3.50
611.0
13.5
14.1
4i
615.0
3.9
653.0
0.78
4.12
670.0
6.4
5.9
4j
585.0
6.1
622.0
0.52
3.72
636.0
8.3
13.5
4k
584.5
4.0
617.0
0.83
5.37
625.0
17.8
2.3
4l
569.0
6.8
604.0
0.53
4.22
612.0
11.2
5.2
1 Abso p ion wa eleng h. 2 Mola abso p ion. 3 Fluo escence wa eleng h. 4 Fluo escence quan um
yield. 5 Fluo escence li e ime. 6 Lasing wa eleng h. 7 Lase e iciency. 8 Pho os abili y, de ined as he
amoun o pumping ene gy abso bed by he dye o e ain 90% o he lase induced emission.
In his ega d, he deco a ion o he a yls g a ed on he ch omopho ic py oles wi h
elec on wi hd awing o elec on eleasing moie ies a he pa a-posi ion is a sui able
app oach o amelio a e he luo escen esponse (Table 2 and Figu e 2). The a achmen o
elec on accep o g oups does no al e he spec al band posi ions, bu p og essi ely
enhances he luo escence e iciency, being wice ha o he o me ones o he dyes
bea ing ca bonyl (4j, Hamme pa ame e σp+ = 0.55) and i luo ome hyl (4h, σp+ = 0.61),
and e en eaching an e iciency o up o 75% o he dye bea ing cyano (4l, σp+ = 0.66), he
s onges elec on wi hd awing uni among he ones es ed so a (Figu e 2). I is wo h
men ioning ha he coexis ence o his las g oup wi h pa a-me hoxy in he 8-phenyl
Figu e 1.
Rep esen a i e abso p ion (o ange) and luo escence ( ed) spec a o he polyphenylBODIPY
4
(see Figu e S1 o he spec a o he es o dyes o his amily) in dilu ed solu ions o cyclohexane.
The co esponding con ou maps o he on ie o bi als a e also enclosed.
Table 2.
Pho ophysical (2
µ
M) and lase (0.5–0.75 mM) p ope ies o he polyphenylBODIPYs in e hyl
ace a e. Full pho ophysical and lase da a in mo e media a e lis ed in Tables S2 and S3, espec i ely.
Dye λab 1
(nm)
εmax·10−4 2
(M−1·cm−1)
λ l3
(nm) φ4τ5
(ns)
λla 6
(nm) %E 7Edose 8
(GJ/mol)
4 577.0 5.0 623.0 0.26 2.28 630.0 8.5 9.0
4g 579.0 5.1 618.0 0.32 2.92 628.0 9.8 9.4
4h 566.5 7.0 597.5 0.47 3.50 611.0 13.5 14.1
4i 615.0 3.9 653.0 0.78 4.12 670.0 6.4 5.9
4j 585.0 6.1 622.0 0.52 3.72 636.0 8.3 13.5
4k 584.5 4.0 617.0 0.83 5.37 625.0 17.8 2.3
4l 569.0 6.8 604.0 0.53 4.22 612.0 11.2 5.2
1
Abso p ion wa eleng h.
2
Mola abso p ion.
3
Fluo escence wa eleng h.
4
Fluo escence quan um yield.
5
Fluo escence li e ime.
6
Lasing wa eleng h.
7
Lase e iciency.
8
Pho os abili y, de ined as he amoun o
pumping ene gy abso bed by he dye o e ain 90% o he lase induced emission.
In his ega d, he deco a ion o he a yls g a ed on he ch omopho ic py oles
wi h elec on wi hd awing o elec on eleasing moie ies a he pa a-posi ion is a sui able
app oach o amelio a e he luo escen esponse (Table 2and Figu e 2). The a achmen
o elec on accep o g oups does no al e he spec al band posi ions, bu p og essi ely
enhances he luo escence e iciency, being wice ha o he o me ones o he dyes bea ing
ca bonyl (
4j
, Hamme pa ame e
σp+
= 0.55) and i luo ome hyl (
4h
,
σp+
= 0.61), and e en
eaching an e iciency o up o 75% o he dye bea ing cyano (
4l
,
σp+
= 0.66), he s onges
elec on wi hd awing uni among he ones es ed so a (Figu e 2). I is wo h men ioning

Molecules 2023,28, 4750 6 o 15
ha he coexis ence o his las g oup wi h pa a-me hoxy in he 8-phenyl inc eases he
cha ge sepa a ion, explaining he sensi i i y o he luo escen esponse o
4l
wi h he
sol en pola i y (down o 48% in ace oni ile, Figu e 2).
Molecules 2023, 28, x FOR PEER REVIEW 6 o 15
inc eases he cha ge sepa a ion, explaining he sensi i i y o he luo escen esponse o
4l wi h he sol en pola i y (down o 48% in ace oni ile, Figu e 2).
Figu e 2. E olu ion o he luo escen e iciency in media o di e en pola i y o ep esen a i e
polyphenylBODIPYs bea ing elec on accep o o elec on dono moie ies a he pa a posi ion o he
pe iphe al py olic phenyls.
I is likely ha his unc ionaliza ion o he a yls wi h elec on ich g oups enhances
he delocaliza ion be ween he dipy in and he phenyls, leading o less single bond
cha ac e in he linkage and he eby dec easing he ee mo ion o he pe iphe al ings. In
ac , heo e ically op imized geome ies a he g ound s a e e eal ha bo h he wis ing
angle and he bond leng h connec ing he phenyls and he py oles, dec ease as he a yls
a e pa a- unc ionalized (a e age alues om 45° o 35° and om 1.45 Å o 1.40 Å,
espec i ely). Fu he e idence o he success o his s a egy o educe in e nal con e sion
is p o ided by 4i and 4k (Figu e 2). E en he sole p esence o he elec onically neu al
ime hylsilane (4i, σp+ = 0.02) yields a ema kable inc ease in he luo escence ha
app oaches 90%. Mo eo e , he elec on dono me hoxy (4k, σp+ = −0.78) induces a u he
ba hoch omic shi and ende s no able luo escence e iciencies eaching almos 100%
(Figu e 2). Howe e , in his case, he ou elec on dono uni s deco a ing he elec on
de icien bo on–dipy in co e we e able o induce cha ge sepa a ion, as sugges ed by he
sol en pola i y igge ed dec ease in he luo escence ou pu (Figu e 2), and he
unexpec ed posi i e sol a och omism o he luo escence band, opposi e o he nega i e
sol a och omism egis e ed o he abso p ion band (Table S2). The e o e, pa a-
unc ionaliza ion o he phenyls deco a ing he ch omopho ic py oles is a good s a egy
o enhance he luo escence signal o poliphenylBODIPYs.
To u he push he spec al bands and each he a - ed–NIR egion he py olic
phenyls we e eplaced by hiophene, ea u ing highe elec on eleasing abili y (σp+ =
−0.43). In ac , he abso p ion band o he poly hiopheneBODIPYs is placed a a ound 630–
650 nm, depending on he meso-phenyl subs i u ion (Table 3). Thus, he highes
ba hoch omic shi is achie ed upon o myla ion o he 8-phenyl (4e), since elec on
wi hd awing g oups a he meso posi ion u he s abilize he LUMO owing o i s high
elec onic densi y loca ed a he ch omopho ic posi ion (Figu e 1). Acco dingly, he
luo escence band is placed a ound 680–710 nm, being again he o myla ed dye 4e, he
one displaying he eddes emission (Figu e 3). Ne e heless, an inc ease in he sol en
pola i y ma kedly a ec ed he luo escence signa u es o his se o
poly hiopheneBODIPYs. O e all, he luo escence e iciency was lowe (a ound 15 o
20%, wi h he excep ion o 4d, which eached almos 40%), han o he polya yla ed
Figu e 2.
E olu ion o he luo escen e iciency in media o di e en pola i y o ep esen a i e
polyphenylBODIPYs bea ing elec on accep o o elec on dono moie ies a he pa a posi ion o he
pe iphe al py olic phenyls.
I is likely ha his unc ionaliza ion o he a yls wi h elec on ich g oups enhances
he delocaliza ion be ween he dipy in and he phenyls, leading o less single bond cha ac-
e in he linkage and he eby dec easing he ee mo ion o he pe iphe al ings. In ac ,
heo e ically op imized geome ies a he g ound s a e e eal ha bo h he wis ing angle
and he bond leng h connec ing he phenyls and he py oles, dec ease as he a yls a e
pa a- unc ionalized (a e age alues om 45
◦
o 35
◦
and om 1.45 Å o 1.40 Å, espec i ely).
Fu he e idence o he success o his s a egy o educe in e nal con e sion is p o ided by
4i
and
4k
(Figu e 2). E en he sole p esence o he elec onically neu al ime hylsilane (
4i
,
σp+
= 0.02) yields a ema kable inc ease in he luo escence ha app oaches 90%. Mo eo e ,
he elec on dono me hoxy (
4k
,
σp+
=
−
0.78) induces a u he ba hoch omic shi and en-
de s no able luo escence e iciencies eaching almos 100% (Figu e 2). Howe e , in his case,
he ou elec on dono uni s deco a ing he elec on de icien bo on–dipy in co e we e
able o induce cha ge sepa a ion, as sugges ed by he sol en pola i y igge ed dec ease in
he luo escence ou pu (Figu e 2), and he unexpec ed posi i e sol a och omism o he luo-
escence band, opposi e o he nega i e sol a och omism egis e ed o he abso p ion band
(Table S2). The e o e, pa a- unc ionaliza ion o he phenyls deco a ing he ch omopho ic
py oles is a good s a egy o enhance he luo escence signal o poliphenylBODIPYs.
To u he push he spec al bands and each he a - ed–NIR egion he py olic
phenyls we e eplaced by hiophene, ea u ing highe elec on eleasing abili y
(σp+=−0.43)
.
In ac , he abso p ion band o he poly hiopheneBODIPYs is placed a a ound 630–650 nm,
depending on he meso-phenyl subs i u ion (Table 3). Thus, he highes ba hoch omic shi
is achie ed upon o myla ion o he 8-phenyl (
4e
), since elec on wi hd awing g oups a
he meso posi ion u he s abilize he LUMO owing o i s high elec onic densi y loca ed
a he ch omopho ic posi ion (Figu e 1). Acco dingly, he luo escence band is placed
a ound 680–710 nm, being again he o myla ed dye
4e
, he one displaying he eddes
emission (Figu e 3). Ne e heless, an inc ease in he sol en pola i y ma kedly a ec ed
he luo escence signa u es o his se o poly hiopheneBODIPYs. O e all, he luo escence
e iciency was lowe (a ound 15 o 20%, wi h he excep ion o
4d
, which eached almos
40%), han o he polya yla ed analogues in apola media. An inc ease in he sol en
Molecules 2023,28, 4750 7 o 15
pola i y implies a p onounced quenching o he emission, as e lec ed in he low e iciencies
(down o 2%) and as li e imes (hund eds o picoseconds) eco ded (Table 3 s. Table 2).
Mo eo e , he luo escen band displays a ma ked ba hoch omic shi (a ound 30 nm) wi h
he sol en pola i y (Table 3and Figu e 3). Such an en i onmen s abilizes he cha ge
sepa a ion and a da k cha ge sepa a ed s a e (CS) can be popula ed. Thus,
4e
showing
push–pull ea u es, emi s a 735 nm in pola media (Figu e 3), he eddes emission he ein
eco ded, bu wi h low luo escence (jus 2%, Table 3). The e o e, he elec on eleasing
abili y o he hiophenes is able o induce cha ge ans e (CT) cha ac e o he emi ing
s a e, becoming a s a e o high pola i y.
Table 3.
Pho ophysical (2
µ
M) p ope ies, in sol en s o di e en pola i y; cyclohexane (c-hex),
e hyl ace a e (E OAc) and ace oni ile (ACN), and lase (0.5–0.75 mM) p ope ies in e hyl ace a e
o he poly hiopheneBODIPYs. Full pho ophysical and lase da a in mo e media a e lis ed in
Tables S4 and S5, espec i ely.
Dye Sol en λab 1
(nm)
εmax·10−4 2
(M−1·cm−1)
λ l3
(nm) φ4τ5
(ns)
λla 6
(nm) %E 7Edose 8
(GJ/mol)
c-hex 638.5 6.0 688.0 0.16 3.47
4a E OAc 630.0 5.0 700.5 0.08 1.07 717.0 11.8 1.3
ACN 624.5 4.1 711.5 0.03 0.42
c-hex 636.0 4.0 682.0 0.20 3.83
4b E OAc 628.0 3.4 695.0 0.09 1.23 712.0 11.4 6.0
ACN 621.5 3.0 707.0 0.03 0.50
c-hex 639.0 5.3 685.5 0.21 3.85
4c E OAc 632.5 4.6 696.0 0.11 1.32 710.0 9.3 7.6
ACN 627.0 4.1 705.5 0.04 0.55
c-hex 629.0 6.5 678.5 0.39 4.10
4d E OAc 625.0 5.1 690.0 0.15 1.41 705.0 20.5 10.0
ACN 619.0 4.2 703.5 0.05 0.62
c-hex 650.0 4.8 708.0 0.17 1.65
4e E OAc 639.0 4.1 721.0 0.04 0.41 744.0 8.7 7.6
ACN 634.5 3.3 736.0 0.02 0.41
1
Abso p ion wa eleng h.
2
Mola abso p ion.
3
Fluo escen wa eleng h.
4
Fluo escence quan um yield.
5
Fluo es-
cence li e ime.
6
Lasing wa eleng h.
7
Lase e iciency.
8
Pho os abili y, de ined as he amoun o pumping ene gy
abso bed by he dye o e ain 90% o he lase induced emission.
Molecules 2023, 28, x FOR PEER REVIEW 7 o 15
analogues in apola media. An inc ease in he sol en pola i y implies a p onounced
quenching o he emission, as e lec ed in he low e iciencies (down o 2%) and as
li e imes (hund eds o picoseconds) eco ded (Table 3 s. Table 2). Mo eo e , he
luo escen band displays a ma ked ba hoch omic shi (a ound 30 nm) wi h he sol en
pola i y (Table 3 and Figu e 3). Such an en i onmen s abilizes he cha ge sepa a ion and
a da k cha ge sepa a ed s a e (CS) can be popula ed. Thus, 4e showing push–pull ea u es,
emi s a 735 nm in pola media (Figu e 3), he eddes emission he ein eco ded, bu wi h
low luo escence (jus 2%, Table 3). The e o e, he elec on eleasing abili y o he
hiophenes is able o induce cha ge ans e (CT) cha ac e o he emi ing s a e, becoming
a s a e o high pola i y.
Figu e 3. No malized abso p ion and luo escence (shadow illed) spec a o 4e as a ep esen a i e
dye o he poly hiopheneBODIPYs (see Figu e S2 o he spec a o he es o dyes o his amily) in
dilu ed solu ions.
Table 3. Pho ophysical (2 μM) p ope ies, in sol en s o di e en pola i y; cyclohexane (c-hex), e hyl
ace a e (E OAc) and ace oni ile (ACN), and lase (0.5–0.75 mM) p ope ies in e hyl ace a e o he
poly hiopheneBODIPYs. Full pho ophysical and lase da a in mo e media a e lis ed in Table S4 and
S5, espec i ely.
Dye Sol en
λ
ab
1
(nm)
ε
max
∙10
−4
2
(M
−1
∙cm
−1
)
λ
l
3
(nm)
ф 4
τ
5
(ns)
λ
la
6
(nm)
%E 7
E
dose
8
(GJ/mol)
c-hex
638.5
6.0
688.0
0.16
3.47
4a
E OAc
630.0
5.0
700.5
0.08
1.07
717.0
11.8
1.3
ACN
624.5
4.1
711.5
0.03
0.42
c-hex
636.0
4.0
682.0
0.20
3.83
4b
E OAc
628.0
3.4
695.0
0.09
1.23
712.0
11.4
6.0
ACN
621.5
3.0
707.0
0.03
0.50
c-hex
639.0
5.3
685.5
0.21
3.85
4c
E OAc
632.5
4.6
696.0
0.11
1.32
710.0
9.3
7.6
ACN
627.0
4.1
705.5
0.04
0.55
c-hex
629.0
6.5
678.5
0.39
4.10
4d
E OAc
625.0
5.1
690.0
0.15
1.41
705.0
20.5
10.0
ACN
619.0
4.2
703.5
0.05
0.62
c-hex
650.0
4.8
708.0
0.17
1.65
4e
E OAc
639.0
4.1
721.0
0.04
0.41
744.0
8.7
7.6
ACN
634.5
3.3
736.0
0.02
0.41
1 Abso p ion wa eleng h. 2 Mola abso p ion. 3 Fluo escen wa eleng h. 4 Fluo escence quan um
yield. 5 Fluo escence li e ime. 6 Lasing wa eleng h. 7 Lase e iciency. 8 Pho os abili y, de ined as he
amoun o pumping ene gy abso bed by he dye o e ain 90% o he lase induced emission.
Figu e 3.
No malized abso p ion and luo escence (shadow illed) spec a o
4e
as a ep esen a i e
dye o he poly hiopheneBODIPYs (see Figu e S2 o he spec a o he es o dyes o his amily) in
dilu ed solu ions.
Molecules 2023,28, 4750 8 o 15
Such a ea u e can be en isaged om Figu e 4. The g a ing o elec on ich hiophene
leads o a mo e ex ended
π
-sys em, sus ained by he simula ed HOMO con ou map,
whe e he
π
-elec onic densi y is clea ly spanned o e he whole molecule, comp ising bo h
BODIPY and hiophenes. Howe e , he exci a ion implies a ma ked elec onic ans e om
he hiophenes o he BODIPY co e, as suppo ed by he heo e ically p edic ed LUMO,
which is mainly loca ed a he la e moie y. Fu he mo e, upon o myla ion o he 8-phenyl,
he shi o he elec onic densi y owa ds he BODIPY is mo e p onounced, eaching he
8- o myla ed ing, owing o he elec on wi hd awing e ec o his unc ionaliza ion. Thus,
his elec onic ea angemen upon exci a ion an icipa es he CT cha ac e o he emi ing
s a e, s eng hened in
4e
. The e o e, poly hiopheneBODIPYs enable us o push he emission
deepe in o he a - ed–NIR egion (beyond 700 nm), bu in u n he e iciency dec eases,
owing o he lowe ene gy gap and he sol en exe ed s abiliza ion o cha ge sepa a ion.
Molecules 2023, 28, x FOR PEER REVIEW 8 o 15
Such a ea u e can be en isaged om Figu e 4. The g a ing o elec on ich hiophene
leads o a mo e ex ended π-sys em, sus ained by he simula ed HOMO con ou map,
whe e he π-elec onic densi y is clea ly spanned o e he whole molecule, comp ising
bo h BODIPY and hiophenes. Howe e , he exci a ion implies a ma ked elec onic
ans e om he hiophenes o he BODIPY co e, as suppo ed by he heo e ically
p edic ed LUMO, which is mainly loca ed a he la e moie y. Fu he mo e, upon
o myla ion o he 8-phenyl, he shi o he elec onic densi y owa ds he BODIPY is mo e
p onounced, eaching he 8- o myla ed ing, owing o he elec on wi hd awing e ec o
his unc ionaliza ion. Thus, his elec onic ea angemen upon exci a ion an icipa es he
CT cha ac e o he emi ing s a e, s eng hened in 4e. The e o e, poly hiopheneBODIPYs
enable us o push he emission deepe in o he a - ed–NIR egion (beyond 700 nm), bu
in u n he e iciency dec eases, owing o he lowe ene gy gap and he sol en exe ed
s abiliza ion o cha ge sepa a ion.
Figu e 4. Con ou maps o he on ie molecula o bi als calcula ed om op imized g ound s a e
geome ies (wb97xd/6-311 + g*) o ep esen a i e polyphenylBODIPY 4 , and
poly hiopheneBODIPYs 4b and 4e. The co esponding heo e ically p edic ed abso p ion spec a
( d wb97xd) a e also depic ed.
Mo i a ed by he ongoing CT upon a achmen o hiophene, we es ed he iabili y
o hese poly hiopheneBODIPYs as halogen- ee single oxygen pho osensi ize s. One o
he mos cu en ly ac i e in pho odynamic he apy is he p omo ion o CT as an
in e media e o each he a ge iple s a e, which enables single oxygen gene a ion [37].
In ac , hiophene- used BODIPYs we e epo ed o pho osensi ize single oxygen h ough
ICT-media ed in e sys em c ossing [38,39]. Howe e , in he he ein epo ed BODIPYs
bea ing di ec ly linked iophenes, no single oxygen emission was de ec ed, nei he unde
d as ic condi ions (dye concen a ion, exci a ion sou ces) no in di e en sol en s whe e
he single oxygen li e ime is longe ( oluene, chlo o o m). I is no ewo hy ha he iple
s a e popula ion om a CT implies a sub le balance be ween CS and cha ge ecombina ion
(CR). In o he wo ds, enough CS should be p omo ed o s abilize he CT s a e, bu a he
same ime, he CR p obabili y should be high enough o a e wa ds popula e he iple
s a e [40]. In he BODIPYs desc ibed he e, such es ained balance is displaced o CS
owing o he simul aneous p esence o ou elec on dono pe iphe al hiophenes. Thus,
he iple s a e is no eached om he CT and he exci a ion ene gy is dissipa ed h ough
Figu e 4.
Con ou maps o he on ie molecula o bi als calcula ed om op imized g ound s a e
geome ies (wb97xd/6-311 + g*) o ep esen a i e polyphenylBODIPY 4 , and poly hiopheneBOD-
IPYs
4b
and
4e
. The co esponding heo e ically p edic ed abso p ion spec a ( d wb97xd) a e
also depic ed.
Mo i a ed by he ongoing CT upon a achmen o hiophene, we es ed he iabili y o
hese poly hiopheneBODIPYs as halogen- ee single oxygen pho osensi ize s. One o he
mos cu en ly ac i e in pho odynamic he apy is he p omo ion o CT as an in e media e
o each he a ge iple s a e, which enables single oxygen gene a ion [
37
]. In ac ,
hiophene- used BODIPYs we e epo ed o pho osensi ize single oxygen h ough ICT-
media ed in e sys em c ossing [38,39]. Howe e , in he he ein epo ed BODIPYs bea ing
di ec ly linked iophenes, no single oxygen emission was de ec ed, nei he unde d as ic
condi ions (dye concen a ion, exci a ion sou ces) no in di e en sol en s whe e he single
oxygen li e ime is longe ( oluene, chlo o o m). I is no ewo hy ha he iple s a e
popula ion om a CT implies a sub le balance be ween CS and cha ge ecombina ion (CR).
In o he wo ds, enough CS should be p omo ed o s abilize he CT s a e, bu a he same
ime, he CR p obabili y should be high enough o a e wa ds popula e he iple s a e [
40
].
In he BODIPYs desc ibed he e, such es ained balance is displaced o CS owing o he
simul aneous p esence o ou elec on dono pe iphe al hiophenes. Thus, he iple s a e
is no eached om he CT and he exci a ion ene gy is dissipa ed h ough non- adia i e
unnels, leading o luo escence quenching and no single oxygen gene a ion.
Molecules 2023,28, 4750 9 o 15
2.3. Lase P ope ies
The absence o popula ion o he iple mani old p omp ed us o es hese ex ended
BODIPYs as pho oac i e media o unable o ganic lase s. All o hem show he ypical
b oad dye lase emission ( ull wid h a hal maximum, FWHM, o e all a ound 5 nm) in
he ed–NIR edge o he isible, anging om 600 nm o 760 nm (Figu e 5), a e being
ans e sally pumped by a wa eleng h- unable Op ical Pa ame ic Oscilla o (OPO), which
allows i adia ion o each dye a i s maximum abso p ion wa eleng h (see Sec ion 3 o
de ails). The concen a ion ha op imizes he lase e iciency, unde s ood as he a io
o he ou pu and inpu (pump) ene gies, depends on each dye (a ound 0.5–0.75 mM,
Tables S3 and S5). In his sense, he lase ou pu e iciency inc eases wi h he concen a ion
up o a maximum pla eau, om which i dec eases owing o eabso p ion/ eemission
phenomena. The shi o he emission peak o longe wa eleng hs wi h he concen a ion
inc ease backs up his in e p e a ion (Tables S3 and S5). In gene al e ms, he e olu ion o
he lase wa eleng h co ela es well wi h he luo escen one (Tables 2and 3). Thus, wi hin
he polya yla ed dyes,
4i
, unc ionalized wi h me hoxy, shows he eddes lase emission
( om a ound 610–635 nm o 670 nm). Al e na i ely, he lase emission o he BODIPYs
unc ionalized wi h hiophene is pushed deepe in o he ed (a ound 705–715 nm), mainly
wi h he p esence o o myl in he 8-phenyl (
4e
, up o 745 nm), being he eddes one among
all he es ed lase dyes.
Molecules 2023, 28, x FOR PEER REVIEW 10 o 15
Figu e 5. Lase spec a scaled by he maximum e iciency o ep esen a i e polyphenylBODIPYs
and poly hiopheneBODIPYs in e hyl ace a e o highligh he co e ed spec al window.
Rega ding he pho os abili y, desc ibed as he equi ed ene gy o dec ease he lase
induced luo escence (LIF) by 10% (see Sec ion 3 o de ails), ex emely high alues a e
no expec ed owing o he con o ma ional eedom o he molecula s uc u e, which
could enhance he dissipa ion o he pumping ene gy as hea . The i luo ome hyl (4h) is
he mos sui ed unc ionaliza ion o enhance he s abili y agains i adia ion o
polyphenylBODIPYs (Table 2). Indeed, his dye holds an op imal balance be ween lase
e iciency (13.5%) and pho os abili y (14.1 GJ/mol). In his sense, i is no ewo hy ha he
low pho os abili y o o he dyes is cha ac e ized by high emission e iciencies (4l and
mainly 4i, bo h sha ing 8-anisole). I has been epo ed ha he 8-posi ion is in ol ed in
he pho obleaching mechanism, and i s subs i u ion ( o ins ance wi h phenyl) is
ecommended o enhance pho os abili y [42,43]. Howe e , i seems ha he pa a-
unc ionaliza ion o his ing wi h he elec on dono me hoxy is de imen al in e ms o
pho os abili y. Al e na i ely, he poly hiopheneBODIPYs show lowe pho os abili y,
being in mos o hem a ound 6–7 GJ/mol and eaching 10 GJ/mol o 4d (Table 3). This
dye is he one wi h he lowes non- adia i e deac i a ion a e cons an o he se ies (Table
S4), which is also e lec ed in i s highe luo escence and lase e iciency (Table 3).
In e es ingly, 4d dye bea s 8-anisole and he pho os abil y inc eases in con as o he
end obse ed abo e wi h polyphenylBODIPYs (4i). This inding e eals ha i is
challenging o es ablish gene al ules o unde s and he in e play be ween molecula
s uc u e and pho os abili y. O he comme cial dyes lasing in his spec al egion, like he
oxazine Nile Blue, main ain 90% o he lase ou pu a e endu ing 10 GJ/mol, simila o
he he ein epo ed polyphenyl and poly hiopheneBODIPYs, which hence can be
ca alogued as compe i i e b igh and long-las ing ac i e media o lase s.
3. Ma e ials and Me hods
3.1. Syn hesis De ails
1H and 13C NMR spec a we e eco ded on a B uke Ad ance III spec ome e (500 o
400 MHz) in deu e iochlo o o m (CDCl3) wi h ei he e ame hylsilane (TMS) (0.00 ppm
1H, 0.00 ppm 13C) o chlo o o m (7.26 ppm 1H, 77.00 ppm 13C) o as in e nal e e ence
unless o he wise s a ed. Da a a e epo ed in he ollowing o de : chemical shi in pa s
pe million (ppm), mul iplici ies (b (b oadened), s (single ), d (double ), ( iple ), q
(qua e ), sex (sex e ), hex (hex e ), m (mul iple ), exch (exchangeable), and app
(appa en )), coupling cons an s, J (Hz), and in eg a ion. In a ed spec a we e eco ded on
a Pe kin-Elme -Spec um 100 FTIR spec opho ome e . Peaks a e epo ed (cm−1) wi h he
ollowing ela i e in ensi ies: s (s ong, 67–100%), m (medium 40–65%), and w (weak 20–
39%). Mel ing poin s we e de e mined on a S an o d Resea ch Sys ems EZ-Mel appa a us
Figu e 5.
Lase spec a scaled by he maximum e iciency o ep esen a i e polyphenylBODIPYs and
poly hiopheneBODIPYs in e hyl ace a e o highligh he co e ed spec al window.
The polyphenyla ed dye
4
, shows a lase e iciency app oaching 10%, which is amelio-
a ed upon pa a-subs i u ion o he py olic phenyls. Thus, he unc ionaliza ion wi h cyano
(
4l
), i luo ome hyl (
4h
) and ime hylsilane (
4k
) inc eases he lase ac ion (up o almos
18% o he la e , being almos wice ha o he e e ence dye
4
), in good co ela ion wi h
he obse ed inc ease in he luo escen esponse o hese dyes (Table 2). The excep ion o
he ule is
4i
, whe e in spi e o i s high luo escen e iciency, he lase e iciency dec eases.
Likely, he cha ge ans e induced by he me hoxy g oups could accoun o his appa en
misma ch. On he o he hand, he poly hiopheneBODIPYs show an unexpec edly high
lase e iciency in iew o he eco ded low luo escence e iciencies (Table 3). Thus, hey
show a mo e s uc u ed and b oade (FWHM up o 10 nm) band wi h an e iciency a ound
10%, eaching 20% o
4d
, in line wi h he highe luo escence esponse eco ded o his
dye. We should bea in mind ha his se o dyes a e cha ac e ized by la ge S okes shi s
(a ound 1500 cm
−1
, Table S4), which dec ease he eabso p ion/ eemission phenomena,
and hence he losses in he esona o ca i y. Thei emi ing s a e is endowed wi h sub-
s an ial CT cha ac e , leading o lowe luo escence e iciencies bu sho e li e imes (down
o 1 ns). Such as decay seems o amelio a e he popula ion in e sion and enhance he
s imula ed emission p obabili y, coun e balancing hei low p obabili y o spon aneous
emission. Indeed, s y yl dyes (i.e., he comme cial LDS722), which a e also cha ac e ized