Planar and Helical Dinaphthophenazines

Plana and Helical Dinaph hophenazines
Fengkun Chen, Manuel Melle-F anco, and Au elio Ma eo-Alonso*
Ci e This: J. O g. Chem. 2022, 87, 7635−7642
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sıSuppo ing In o ma ion
ABSTRACT: In his s udy, we epo he syn hesis o a se ies o plana
and helical dinaph hophenazines by cyclocondensa ion eac ions
be ween he newly de eloped 9,10-bis(( iisop opylsilyl)e hynyl)-
an h acene-1,2-dione and diffe en diamines. Thei op oelec onic and
elec ochemical p ope ies a e s udied by ul a iole − isible (UV− is)
spec oscopy, fluo escence spec oscopy, cyclic ol amme y, and
densi y unc ional heo y calcula ions.
■INTRODUCTION
Nonplana polycyclic a oma ic hyd oca bons (PAHs) and
nanog aphenes possess pa icula op oelec onic p ope ies
ha a e de i ed om hei nonplana π-conjuga ion and
unique in e molecula π-con ac s.
1
Helicenes
1e−h
and wis acenes
1d,g,h
(Figu e 1a) a e some o
he mos ep esen a i e nonplana PAHs and ha e a ac ed
conside able a en ion as op oelec onic ma e ials o pola ized
ligh emi e s and de ec o s,
2
nonlinea op ics
3
and spin-
onics,
4
e c. Helicenes and wis acenes a e helical sys ems ha
diffe in he di ec ion o he helix p opaga ion axis ha is
imposed by he a angemen o he ings in he a oma ic co e
(Figu e 1a). Helicenes consis o angula ly o ho-annula ed
ings in a helical a angemen along he axis pe pendicula o
he ings, as a esul o he s e ic in e ac ions be ween e minal
a oma ic ings, while wis acenes consis o linea o ho-
annula ed ings and exhibi a helical s uc u e along he axis
pa allel o he ings, as a esul o he s e ic in e ac ions
be ween s e ically demanding pe iphe al subs i uen s.
The e is ano he class o helical a oma ics ha combines
bo h angula ly and linea ly annula ed ings. Examples o hese
include he molecula spi al s ai case,
5
molecula hai pins,
6
and
π-expanded helicenes
7
(Figu e 1b). In hese e ms, dinaph-
hophenazines a e a amily o compounds ha combine linea
and angula annula ions and ha ha e ecei ed li le a en ion.
The diffe en a angemen s o hei used ings can gi e ise o
Z-shaped (dinaph ho[a,h]phenazine) o U-shaped (dinaph ho-
[a,j]phenazine) isome s. Howe e , he e is a limi ed numbe o
me hods o ob ain hese s uc u es. The Z-shaped dinaph-
hophenazine has been ob ained by he oxida i e annula ion o
aminoan h acenes (Cha 1a).
8
Meanwhile, he U-shaped
dinaph ho[a,j]phenazine has been ob ained by he oxida i e
ea angemen o bian h yldiamines (Cha 1b).
9
In bo h cases,
he ou es yielded plana dinaph hophenazines. Howe e , he
U-shaped isome s, i p ope ly unc ionalized, can gi e ise o π-
expanded helicenoids.
10
Recei ed: Janua y 19, 2022
Published: May 26, 2022
Figu e 1. (a) Gene al s uc u e o helicenes and wis acenes. (b)
Examples o p e iously epo ed hyb id helical a oma ics, including a
molecula “spi al s ai case,”
5
a molecula “hai pin”,
6b
and a π-
expanded helicene.
7c
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Cyclocondensa ion eac ions be ween o-quinone and o-
diamine p ecu so s ha e been widely used o he cons uc ion
o ni ogen-doped PAHs, nanog aphenes, and wo-dimensional
(2D) polyme s.
11
Howe e , despi e hese ad ances and he
possibili ies offe ed by cyclocondensa ion eac ions o p epa e
nonplana sys ems, his app oach has no been explo ed in he
syn hesis o dinaph hophenazines. He ein, we desc ibe a
syn he ic ou e o he syn hesis o diffe en dinaph hophena-
zines by means o cyclocondensa ion eac ions (Cha 1c).
This ou e p o ides a mix u e o he Z- and U-shaped
s uc u al isome s ha can be isola ed by ch oma og aphy. The
Z-shaped dinaph hophenazines a e almos plana because he e
is no s e ic in e ac ion be ween he bulky iisop opylsilyl
(TIPS) subs i uen s. Whe eas, he U-shaped dinaph hophena-
zines adop a π-expanded helicene s uc u e as a esul o he
s e ic in e ac ions be ween TIPS g oups ha poin o he
cen e o he helix.
■RESULTS AND DISCUSSION
The syn hesis o he a ge dinaph hophenazines 1and 2
equi es he syn hesis o app op ia e o-dione and o-diamine
building blocks (Scheme 1). An h acene-1,2-dione 4was
syn hesized om 2-hyd oxy-9,10-bis( iisop opylsilyle hynyl)-
an h acene 3, as shown in Scheme 1a. T ea men o 3wi h
phenylseleninic anhyd ide as an oxidan p o ided 4in a 94%
yield. Diamine 6was gene a ed by educ ion o 5wi h LiAlH4
in die hyl e he a 0 °C. Due o he limi ed s abili y, amine 6
was no pu ified and i was used di ec ly in he nex s ep. The
cyclocondensa ion o amine 6wi h dione 4in a 1:1 mix u e o
AcOH/CHCl3in efluxing condi ions affo ded 1-Z and 1-U
wi h yields o 34% and 36%, espec i ely, bo h as yellowish
solids a e ch oma og aphic pu ifica ion (Scheme 1b).
To expand he lib a y o dinaph hophenzines and o es he
e sa ili y o he p ecu so s, dione 4was condensed wi h 1,2-
diaminoan h acene-9,10-dione 7unde he same condi ions
men ioned abo e (Scheme 1c). The wo s uc u al isome s,
namely, 2-Z (31%) and 2-U (44%), we e ob ained as ed solids
a e pu ifica ion by column ch oma og aphy.
The s uc u es o 1-Z,1-U,2-Z, and 2-U we e confi med by
1H NMR, 1H−1H COSY, 13C NMR spec a, and high-
esolu ion mass spec ome y (HR-MS) (de ails a e gi en in
he Suppo ing in o ma ion). The 1H NMR spec a o 1-Z and
1-U in CDCl3displayed symme ic pa e ns. The p o ons a
he K- egions o 1-Z gi e wo double signals a 8.88 and 8.24
ppm wi h he o he h ee mul iple s in he a oma ic egion
assigned o he p o ons in he e minal benzene ings. A simila
1H NMR spec um was obse ed o 1-U bu wi h sepa a e
signals o he dias e eo opic TIPS g oups. The 1H NMR
spec a o 2-Z and 2-U show a mo e complex se o signals
consis en wi h he s uc u e (de ails a e gi en in he
Suppo ing in o ma ion). In he case o 2-U, he signals o
he inne TIPS g oup appea o be shi ed upfield as a esul o
aniso opy because his TIPS g oup si s on op o one o he
ca bonyls o he quinone.
The elec onic abso p ion spec a o he naph ophenazines
e idenced diffe ences in hei op oelec onic p ope ies. In he
case o 1-Z and 1-U,diffe en abso p ion spec a we e
obse ed, in which he longes -wa eleng h abso p ion is
sligh ly ed-shi ed o 1-U (Figu e 2a). In he case o 2-Z
and 2-U, a simila pa e n was obse ed ha esembles he
pa e n o he abso p ion spec um o 1-U bu wi h he
p esence o a b oad band be ween 450 and 600 nm (Figu e
2b). This addi ional band, which is also sligh ly ed-shi ed in
he case o 2-U, is consis en wi h an in amolecula cha ge
ans e p ocess. The op ical HOMO−LUMO gaps de e -
mined om he onse o he lowes -ene gy abso p ion show
simila alues o he 1-Z (2.41 eV)/1-U (2.38 eV) and 2-Z
(2.12 eV)/2-U (2.09 eV) couples (Table 1).
Sha p and ib onically esol ed fluo escence spec a we e
eco ded o 1-Z (510 nm) and 1-U (518 nm) wi h high
quan um yields (0.83 and 0.61, espec i ely) (Figu e 2c and
Table 1). The high quan um yield o 1-Z is in ag eemen wi h
hose obse ed on pa en double π-expanded helicenes.
10
The
lowe quan um yield obse ed o 1-U also ag ees wi h
p e ious epo s ha desc ibe lowe fluo escence quan um
yields o wis ed sys ems.
12
2-Z and 2-U showed no
fluo escence, which is consis en wi h a nonemissi e in a-
molecula cha ge ans e ansi ion (also see he heo y
sec ion below).
Elec ochemical p ope ies we e s udied by cyclic ol am-
me y measu emen s in o-dichlo obenzene using nBu4NPF6as
an elec oly e. The ol ammog ams in all cases displayed one
educ ion and wo oxida ion p ocesses (Figu e 2d). The edox
po en ials a e summa ized in Table 1. Compounds 1-Z and 1-
Ushowed an iden ical oxida ion po en ial a +0.9 V and a
educ ion po en ial a a ound −1.9 V, which is sligh ly mo e
Cha 1. Diffe en App oaches o Dinaph hophenazines
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nega i e o 1-U. Whe eas, 2-Z and 2-U displayed a e y
simila oxida ion po en ial a a ound +1.1 V and he same
educ ion po en ial a −1.25 V. The elec ochemical highes -
occupied molecula o bi al (HOMO) (ioniza ion po en ials)
and helowes -unoccupiedmolecula o bi al(LUMO)
(elec on affini ies) we e es ima ed om he onse o he
fi s oxida ion and educ ion wa es, espec i ely (Table 1).
The HOMO le els a e he same o 1-Z and 1-U (−5.44 eV),
whe eas he HOMO le el o 2-Z (−5.66 eV) is sligh ly lowe
han ha o 2-U (−5.58 eV). The LUMO le els a e e y
simila in he case o 1-Z (−3.21 eV) and 1-U (−3.15 eV).
The ene gy o LUMO d ops when a quinone is p esen in he
a oma ic amewo k 2-Z (−3.97 eV) and 2-U (−3.91 eV). The
elec ochemical HOMO−LUMO gaps o 1-Z (2.23 eV)/1-U
(2.29 eV) and 2-Z (1.69 eV)/2-U (1.67 eV) couples show he
same ends as he op ical HOMO−LUMO gaps.
A e se e al a emp s, we we e unable o g ow single
c ys als sui able o X- ay diff ac ion, so we elied on
calcula ions o ge an insigh in o hei s uc u es. The
op imized geome ies we e calcula ed a he B3LYP/6-
31G(d,p) le el (Figu es 3aandS1). Fo compa ison,
op imized s uc u es wi h he same Hamil onian augmen ed
by a dispe sion co ec ion we e also compu ed yielding almos
iden ical esul s (Figu e S2 and Table S1). Dinaph hophena-
zine 1-Z is i ually plana wi h small wis s, in ag eemen wi h
a p e iously epo ed c ys al s uc u e.
8
Con e sely, 1-U
adop s a helical s uc u e due o he s e ic hind ance esul ing
om he bulky TIPS g oups in he inne im. The s uc u e o
1-U shows la ge o sion angles along he BCD/B′C′D′ ings
(21.5 and 20.7°, espec i ely, Figu e S1) ha oge he p oduce
a helix angle o 42.2°. This helical s uc u e and he helix angle
alue is consis en wi h he s uc u es and helix angles
Scheme 1. Syn he ic Rou es
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obse ed on a pa en double π-expanded helicene (40.6°)
10
and wi h hose o a simila amily o less-s ained π-expanded
helicenoids (28°).
13
In he case o he quinone se ies,
dinaph hophenazine 2-Z is no as plana as 1-Z. Simila ly,
compound 2-U also shows a helical s uc u e wi h o sion
angles along he BCD/B′C′D′ ings (15.0 and 16.2°,
espec i ely) ha a e lowe han hose obse ed in 1-U. This
is because o he lowe s ained s uc u e as a esul o only one
TIPS−ace ylene g oup in he inne im, which gene a es a
smalle helix angle o 31.2°. The con o ma ional s abili y o he
1-U and 2-U was in es iga ed a he x b-GFN1 le el wi h a
me adynamics p ocedu e. In he case o 1-U, no e idence o
acemiza ion was obse ed, as nei he me adynamics no
nudge elas ic band me hodologies p oduced a chemically
sensible pa h o his p ocess. This is consis en wi h he la ge
o e lap be ween he wo TIPS g oups ha p ac ically locks he
s uc u e. Whe eas, in he case o 2-U, he acemiza ion is
possible, as illus a ed by a ela i ely low ba ie (96 kJ/mol,
Figu e S3).
Based on he bond leng h analysis and on he local
a oma ici y indica ed by he nuclea independen chemical
shi (NICS) alues (Figu e 3a), he dominan esonance
s uc u es a e bes ep esen ed by Cla ’s sex e ule. In he case
o 1-Z and 1-U, he dominan elec onic s uc u e consis s o
wo K- egions (C and C′) wi h a double bond cha ac e (bond
leng hs ∼1.35 Å), wo naph halene g oups (AB and A′B′), and
a py azine (D) g oup. Fo ins ance, he lowes NICS (0) alues
o 1-Z and 1-U (indica ed in each ing o Figu e 3a) we e
ound on he naph halene and py azine g oups, while NICS
(0) alues close o ze o we e ound on he ings o he K-
egions. Meanwhile, in he case o 2-Z and 2-U, he dominan
elec onic s uc u e consis s o wo K- egions (C and C′) wi h
a double bond cha ac e (bond leng hs ∼1.35−1.37 Å), a
naph halene g oup (A′B′), a benzene g oup (A), a py azine
(D) g oup, and a quinone (B) g oup. In he case o 2-Z and 2-
U, he lowes NICS (0) alues (indica ed in each ing o Figu e
3a) we e ound on he naph halene (A′B′), py azine (D), and
benzene (A) g oups. One o he K- egion ings shows again a
simila NICS (0) alue app oaching ze o, whe eas he K- egion
ing nex o he quinone ing shows a mo e nega i e alue. The
quinone ings (B′) display posi i e NICS (0) alues, indica ing
hei an ia oma ic cha ac e .
Figu e 2. (a) UV/ is abso p ion spec a o 1-Z and 1-U in CH2Cl2, (b) UV/ is abso p ion spec a o 2-Z and 2-U CH2Cl2, (c) fluo escence
spec a and quan um yields o 1-Z and 1-U in CH2Cl2(λex = 450 nm), and (d) cyclic ol ammog ams in o-dichlo obenzene using nBu4NPF6(0.05
M) as an elec oly e (scan a e: 100 mV/s).
Table 1. Summa y o Op ical, Elec ochemical, and Calcula ed P ope ies
λabs
a
(nm)
λem
a
(nm) Egop
b
(eV) E1/2ox
(V) E1/2 ed
(V) EHOMOc
c
(eV) ELUMOc
c
(eV) Egc
c
(V) EHOMOcal.
d
(eV) ELUMOcal.
d
(eV) Egcal.
d
(eV)
1-Z 498 510 2.41 0.90 −1.89 −5.44 −3.21 2.23 −5.47 −2.75 2.72
1-U 502 518 2.38 0.90 −1.98 −5.44 −3.15 2.29 −5.45 −2.74 2.71
2-Z 529 2.12 1.17 −1.25 −5.66 −3.97 1.69 −5.75 −3.39 2.36
2-U 532 2.09 1.09 −1.25 −5.58 −3.91 1.67 −5.73 −3.38 2.35
a
Abso p ion and emission we e measu ed in CH2Cl2.
b
Op ical band gap was calcula ed using he equa ion Egop = 1240/λo se , whe e λo se is he
offse wa eleng h de i ed om he lowes -ene gy abso p ion band.
c
F on ie molecula o bi als and band gaps om cyclic ol amme y we e
es ima ed as: EHOMOc (eV) = −(Eonse ox −EFc/Fc++ 4.8) (eV), ELUMOc (eV) = −(Eonse ed −EFc/Fc++ 4.8) (eV), and Egc =ELUMOc −EHOMOc .
d
EHOMOcal. and ELUMOcal. we e calcula ed a he B3LYP/6-311+G(2d,p)(CH2Cl2)/B3LYP/6-31G(d,p) le el, and Egcal. was calcula ed as Egcal. =
ELUMOcal. −EHOMOcal..
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Theo e ical calcula ions (B3LYP/6-311+G(2d,p)(CH2Cl2)/
B3LYP/6-31G(d,p)) we e ca ied ou o shine addi ional ligh
on he op oelec onic and edox p ope ies o he dinaph-
hophenazines. The calcula ed ene gy gaps show he same
ends obse ed in he op ical and elec ochemical gaps (Table
1). Acco ding o ime-dependen densi y unc ional heo y
(TD-DFT) calcula ions, he longes -wa eleng h abso p ions o
all o hese compounds we e mainly a ibu ed o he HOMO
→LUMO ansi ions (Table S2). The HOMO and LUMO
o bi als o 1-Z and 1-U a e ho oughly delocalized along he
dinaph ophenazine co e (Figu e 3b,c), whe eas he HOMOs
o 2-Z and 2-U a e mainly loca ed on he iisop opylsilyle-
hynyl-subs i u ed naph ophenazine side. The elec onic
dis ibu ion o he HOMO and he LUMO on diffe en sides
o he dinaph hophenazine co e in he case o 2-Z and 2-U
implies in amolecula cha ge ans e o his exci a ion.
■CONCLUSIONS
In summa y, we ha e desc ibed he syn hesis o plana and
helical dinaph hophenazines by cyclocondensa ion eac ions.
This was achie ed by condensa ion o an h acene-1,2-dione 4,
wi h diffe en diamines. Due o he s e ic in e ac ions aised by
he bulky TIPS g oups, bo h U-shaped dinaph hophenazines
1-U and 2-U show helicenoid s uc u es, whe eas he co e o
he Z-shaped dinaph hophenazines 1-Z and 2-U emains
i ually plana . Op oelec onic cha ac e iza ion e eals diffe -
en abso p ionpa e ns o 1-Z and 1-U bu simila
fluo escence p ope ies wi h high quan um yields (0.83 and
0.61, espec i ely). A diffe en beha io was obse ed on he
quinone con aining 2-Z and 2-U,whichshowssimila
abso p ion pa e ns and he p esence o an addi ional band
consis en wi h a nonemissi e in amolecula cha ge ans e
p ocess. Theo e ical calcula ions a e consis en wi h expe -
imen al obse a ions and indica e ha he p esence o he
used quinone on one o he sides s ongly pola izes he
dinaph hophenazine co e a o ing he cha ge ans e p ocess.
O e all, his wo k p o ides a new ou e o he syn hesis o
dinaph hophenazines and also o new aluable p ecu so s ha
can be used in he syn hesis o o he and mo e complex PAHs
and nanog aphenes.
■EXPERIMENTAL SECTION
Gene al In o ma ion. Comme cially a ailable sol en s and
eagen s we e used wi hou u he pu ifica ion unless o he wise
Figu e 3. (a) Top iew and (b) side iew o he op imized geome ies wi h selec ed bond leng h (Å) and nuclea independen chemical shi
(NICS) (0) alues (in ed) calcula ed a he B3LYP/6-31G(d,p) le el. Bonds a e ende ed in a colo con inuum anging om ed (1.29 Å) o
whi e (1.40 Å) o blue (1.51 Å) so ha Cla ’s a oma ic sex e s a e ligh e /whi e colo s and localized double and single bonds a e ed and blue,
espec i ely. (c) LUMO and (d) HOMO o bi als calcula ed a he B3LYP/6-31G(d,p) le el.
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no ed. Column ch oma og aphy was ca ied ou using a Silica gel 60
om Scha lab. UV/ isible abso p ion spec a we e eco ded on a
Pe kin-Elme Lambda 950 spec ome e . Fluo escence spec a we e
egis e ed on a LS55 Pe kin-Elme Fluo escence spec ome e .1H and
13C NMR spec a we e eco ded on a B uke A ance 400 and 500
spec ome e s a 298 K using pa ially deu e a ed sol en s as in e nal
s anda ds. High- esolu ion a mosphe ic-p essu e-chemical-ioniza ion
ime-o -fligh mass-spec ome y (HR-APCI-TOF-MS) measu e-
men s we e ca ied ou in he Gene al Se ices o he Uni e si y o
he Basque Coun y (SGIke ) in a The mo LCQ Ad an age using
posi i e-ion mode by D . Alicia Sanchez. High- esolu ion ma ix-
assis ed lase deso p ion ioniza ion mass spec ome y (HR-MALDI-
TOF-MS) measu emen s we e ca ied ou in CIC Biomagune in an
Ul aflex III (B uke Dal onics) MALDI-TOF ( equency- ipled (355
nm) Nd:YAG lase ) by D . Ja ie Cal o. Cyclic ol amme y
measu emen s we e ca ied ou on a P ince on Applied Resea ch
Pa s a 2273 in a h ee-elec ode single compa men cell wi h a glassy
ca bon disc wo king elec ode, a pla inum wi e coun e elec ode, and
a sil e wi e pseudo e e ence elec ode. All o he po en ial alues a e
epo ed as E1/2 =(Epa+Epc)/2 in V e sus he edox po en ial o he
e ocene/ e ocenium couple. 6,11-Bis(2-( iisop opylsilyl)e hynyl)-
an h a[2,1-c][1,2,5] hiadiazole (5)
10
and 2-hyd oxy-9,10-bis-
( iisop opylsilyle hynyl)an h acene (3)
14
we e p epa ed acco ding
o epo ed p ocedu es, espec i ely.
Syn hesis o 9,10-Bis(2-( iisop opylsilyl)e hynyl)an h acene-1,2-
dione (4). Asolu iono 3(0.215 g, 0.388 mmol) in d y
e ahyd o u an (THF) (20 mL) was added o a suspension o
phenylseleninic anhyd ide (0.21 g, 70%, 0.582 mmol) in d y THF (50
mL) a 50 °C in an oil ba h unde N2. The eac ion was s i ed a
oom empe a u e o 24 h. Then, he mix u e was dilu ed wi h
dichlo ome hane and washed wi h aqueous NaHCO3. The o ganic
laye was washed wi h wa e and b ine and d ied o e anhyd ous
Na2SO4. A e emo al o he sol en s, he c ude p oduc was pu ified
wi h column ch oma og aphy on silica o ob ain 4(0.21 g, 94%) as
ed solids. 1H NMR (400 MHz, CDCl3, ppm) δ8.75−8.73 (m, 1H),
8.48−8.46 (m, 1H), 8.39 (d, J= 10.2 Hz, 1H), 7.78−7.70 (m, 2H),
6.63 (d, J= 10.2 Hz, 1H), 1.27−1.21 (m, 42H).13C{1H} NMR (101
MHz, CDCl3, ppm) δ181.1, 177.9, 144.3, 135.0, 134.2, 132.6, 131.1,
130.1, 129.9, 129.4, 128.4, 128.2, 126.6, 123.4, 111.6, 107.6, 102.6,
100.6, 18.9, 11.6, 11.5. HR-APCI-TOF-MS: m/zcalcd o
C36H48O2Si2[M + H]+, 569.3271, ound 569.3268.
Syn hesis o 1-Z and 1-U.LiAlH4(5.0 mL, 4 M in die hyl e he ,
20.0 mmol) was added d opwise unde N2 o a ound-bo om flask
cha ged wi h a solu ion o 5(238.5 mg, 0.4 mmol) in d y die hyl
e he (50 mL) a 0 °C. Then, he eac ion mix u e was s i ed a oom
empe a u e o e nigh . Then, he eac ion was quenched wi h
sa u a ed NH4Cl (aq) and ex ac ed wi h dichlo ome hane. The
combined o ganic laye s we e washed wi h wa e and b ine and d ied
o e anhyd ous Na2SO4. A e he emo al o he sol en s, he esidue
was used di ec ly in he nex s ep. A mix u e o ace ic acid/chlo o o m
(30:30 mL) was added o a Schlenk ube cha ged wi h he esidue o
he p e ious s ep and wi h compound 4(113.7 mg, 0.2 mmol). The
eac ion was s i ed a oom empe a u e o 48 h and hen hea ed o
eflux in an oil ba h o 48 h. A e cooling o oom empe a u e, he
eac ion was quenched wi h sa u a ed NH4Cl (aq), and he mix u e
was ex ac ed wi h dichlo ome hane. The combined o ganic laye s
we e washed wi h b ine and d ied o e Na2SO4. A e emo al o he
sol en s, he c ude p oduc was pu ified wi h column ch oma og aphy
on a silica gel wi h hexane/dichlo ome hane (DCM) as an eluen o
ob ain 1-Z (70.6 mg, 32%) and 1-U (80.0 mg, 36%).
1-Z:1H NMR (500 MHz, CDCl3, ppm) δ9.23−9.09 (m, 2H),
8.88 (d, J= 9.5 Hz, 2H), 8.78−8.71 (m, 2H), 8.23 (d, J= 9.5 Hz,
2H), 7.85−7.70 (m, 4H), 1.32−1.30 (m, 84H).13C{1H} NMR (125
MHz, CDCl3, ppm) δ142.6, 141.3, 134.52, 133.49, 133.2, 130.9,
129.2, 128.7, 128.4, 128.1, 127.8, 127.4, 119.8, 119.7, 107.8, 106.2,
105.6, 103.3, 19.2, 19.0, 12.0, 11.7. HR-MALDI-TOF-MS: m/zcalcd
o C72H96N2Si4[M + H]+, 1101.6727, ound 1101.6808.
1-U:1H NMR (500 MHz, CDCl3, ppm) δ8.95−8.89 (m, 2H),
8.78−8.70 (m, 4H), 7.94 (d, J= 9.3 Hz, 2H), 7.77−7.71 (m, 4H),
1.35−1.28 (m, 42H), 0.74−0.69 (m, 18H), 0.63−0.60 (m,
24H).13C{1H} NMR (125 MHz, CDCl3, ppm) δ142.4, 138.7,
134.0, 133.2, 131.5, 129.9, 128.5, 127.9, 127.8, 127.5, 127.2, 120.9,
118.7, 105.7, 105.0, 103.8, 103.1, 19.1, 18.51, 18.47, 11.7, 11.5. HR-
MALDI-TOF-MS: m/zcalcd o C72H96N2Si4[M + H]+, 1101.6727,
ound 1101.6810.
Syn hesis o 2-Z and 2-U.A Schlenk ube was cha ged wi h 4
(0.114 g, 0.2 mmol) and 1,2-diaminoan h aquinone 7(57.13 mg, 0.24
mmol) unde N2. Then, a mix u e o ace ic acid and chlo o o m
(15:15 mL) was added. The mix u e was hea ed o eflux in an oil
ba h and s i ed o 2 days. A e cooling o oom empe a u e, he
mix u e was dilu ed wi h dichlo ome hane, washed wi h wa e and
b ine, and d ied o e Na2SO4. A e e apo a ion o he sol en s,
pu ifica ion o he esidue wi h column ch oma og aphy affo ded 2-Z
(47.5 mg, 31%) and 2-U (67.2 mg, 44%) as ed solids.
2-Z:1H NMR (500 MHz, CDCl3, ppm) δ9.11−9.09 (m, 1H),
8.85 (d, J= 9.6 Hz, 1H), 8.75−8.72 (m, 2H), 8.43−8.41 (m, 1H),
8.33−8.32 (m, 1H), 8.11 (d, J= 9.6 Hz, 1H), 7.89−7.78 (m, 5H),
1.30−1.27 (m, 42H). 13C{1H} NMR (125 MHz, CDCl3, ppm) δ
183.8, 146.9, 145.0, 142.8, 139.9, 135.9, 135.6, 135.2, 134.7, 134.5,
134.2, 133.8, 133.7, 133.2, 132.2, 129.1, 128.9, 128.6, 128.5, 128.3,
127.6, 126.7, 125.9, 121.3, 120.7, 108.8, 106.4, 105.8, 102.4, 19.1,
19.0, 11.9, 11.6. HR-MALDI-TOF-MS: m/zcalcd o C50H52N2O2Si2
[M + H]+, 771.3801, ound 771.3751.
2-U:1H NMR (500 MHz, CDCl3, ppm) δ9.04−9.01 (m, 1H),
8.78−8.69 (m, 3H), 8.53 (d, J= 8.8 Hz, 1H), 8.37−8.34 (m, 2H),
7.88−7.76 (m, 5H), 1.32−1.25 (m, 21H), 0.98−0.92 (m,
21H).13C{1H} NMR (125 MHz, CDCl3, ppm) δ183.8, 181.8,
145.9, 144.8, 144.1, 137.5, 135.1, 135.0, 134.8, 134.7, 134.4, 133.8,
133.6, 133.2, 132.2, 129.8, 129.3, 129.0, 128.8, 128.3, 127.7, 127.5,
127.5, 126.7, 121.8, 120.1, 105.9, 105.3, 104.7, 102.4, 19.0, 18.8, 11.7,
11.6. HR-MALDI-TOF-MS: m/zcalcd o C50H52N2O2Si2[M + H]+,
771.3801, ound 771.3724.
■ASSOCIATED CONTENT
*
sıSuppo ing In o ma ion
The Suppo ing In o ma ion is a ailable ee o cha ge a
h ps://pubs.acs.o g/doi/10.1021/acs.joc.2c00129.
Op imized geome ies, NMR spec a, and calcula ions
(PDF)
■AUTHOR INFORMATION
Co esponding Au ho
Au elio Ma eo-Alonso −POLYMAT, Uni e si y o he
Basque Coun y UPV/EHU, 20018 Donos ia-San Sebas ian,
Spain; Ike basque, Basque Founda ion o Science, 48009
Bilbao, Spain; o cid.o g/0000-0002-5316-2594;
Email: [email p o ec ed]
Au ho s
Fengkun Chen −POLYMAT, Uni e si y o he Basque
Coun y UPV/EHU, 20018 Donos ia-San Sebas ian, Spain
Manuel Melle-F anco −Depa men o Chemis y,
CICECOA ei o Ins i u e o Ma e ials, Uni e si y o
A ei o, 3810-193 A ei o, Po ugal; o cid.o g/0000-0003-
1929-0477
Comple e con ac in o ma ion is a ailable a :
h ps://pubs.acs.o g/10.1021/acs.joc.2c00129
Au ho Con ibu ions
This manusc ip was w i en h ough con ibu ions o all
au ho s, who ha e gi en app o al o he final e sion o he
manusc ip .
No es
The au ho s decla e no compe ing financial in e es .
The Jou nal o O ganic Chemis y pubs.acs.o g/joc A icle
h ps://doi.o g/10.1021/acs.joc.2c00129
J. O g. Chem. 2022, 87, 7635−7642
7640
■ACKNOWLEDGMENTS
A.M.-A. acknowledges suppo o he Basque Founda ion o
Science (Ike basque), POLYMAT, he Uni e si y o he
Basque Coun y, Dipu ación Fo al de Guipuzcoa, Gobie no
Vasco (BERC p og amme) and Gobie no de Espana (P ojec
CEX2020-001067-M financed by MCIN/AEI/10.13039/
501100011033). Technical and human suppo p o ided by
SGIke o UPV/EHU and Eu opean unding (ERDF and ESF)
is acknowledged. This p ojec ecei ed unding om he
Eu opean Resea ch Council (ERC) unde he Eu opean
Union’s Ho izon 2020 Resea ch and Inno a ion P og amme
(g an ag eemen no. 722951). This p ojec ecei ed unding
om he Eu opean Union′s Ho izon 2020 Resea ch and
Inno a ion P og amme unde g an ag eemen nos. 664878
and 899895. F.C. and A.M.-A acknowledge ha his p ojec
ecei ed unding om he Eu opean Union’s Ho izon 2020
Resea ch and Inno a ion P og amme unde he Ma ie
Skłodowska-Cu ie g an ag eemen no. 839626. M.M.-F.
acknowledges suppo om he Po uguese Founda ion o
Science and Technology (FCT), unde he p ojec IF/00894/
2015, and he p ojec CICECO-A ei o Ins i u e o Ma e ials,
FCT e UID/CTM/50011/2019, UIDB/50011/2020, and
UIDP/50011/2020, financed by na ional unds h ough he
FCT/MEC and when app op ia e c-financed by FEDER unde
he PT2020 Pa ne ship Ag eemen .
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