As ea u ed in:
Showcasing esea ch om he g oup o D Ál a ez a
he GIR MIOMeT Labo a o y, IU CINQUIMA/Química
Ino gánica, Facul ad de Ciencias, Uni e sidad de
Valladolid, Valladolid, Spain.
ON/OFF me al- igge ed molecula weeze s o ulle ene
ecogni ion
New molecula weeze s o ulle ene ecogni ion based
on bipy idine-co annulene mo i s ha e been ob ained.
Re e sible and quan i a i e swi ching ON/OFF s a e is
achie ed by me al coo dina ion, allowing he con ol o he
ulle ene ecogni ion capabili y and leading o he o ma ion
o an e ec i e me al- igge ed molecula machine.
See Raúl Ga cía-Rod íguez,
Celedonio M. Ál a ez e al .,
Chem . Commun ., 2021, 57 , 11013.
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Eungje Lee e al .
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Ni
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O
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Pages 10957–11098
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Ci e his: Chem. Commun., 2021,
57, 11013
ON/OFF me al- igge ed molecula weeze s
o ulle ene ecogni ion†
Ad iana Sac is a
´n-Ma ı
´n, ‡He
´c o Ba be o, ‡Se gio Fe e o,
Daniel Miguel, Rau
´l Ga cı
´a-Rod ı
´guez * and Celedonio M. A
´l a ez *
He ein, we epo molecula weeze s o ulle ene ecogni ion
based on 2,20-bipy idine-bea ing co annulene mo i s. The syn o
an i con i ma ion can be selec ed simply by Cu(I) coo dina ion/
decoo dina ion, hus con olling he ulle ene ecogni ion capabil-
i y o he sys em on demand and leading o he o ma ion o
effec i e me al- igge ed ON/OFF molecula weeze s.
S imuli- esponsi e a i icial ma e ials a e syn he ic mul is able sys-
ems capable o ca ying ou a mac oscopic ask a e s imula ion-
induced s uc u e changes o hei componen s a he mic oscopic
le el.
1
Mos o hese a chi ec u es ha e been designed using
mechanisms occu ing in biological species as bluep in s (i.e.,
bioinspi ed design)
2
and mimic na u al p ocesses such as he
allos e ic beha iou p omo ed by chemical effec o s in enzymes, o
ins ance.
3
One in e es ing app oach is he usage o coo dina ion
complex chemis y, which encompasses a as asso men o ansi-
ion me als whose abili y o bind mul iple ligands wi h a wide ange
o affini ies allows he o ma ion o complex sys ems.
4
Such affi-
ni ies can be modula ed and u ilized in coo dina ion–decoo dina-
ion schemes ha ul ima ely modi y hei s uc u e, gi ing ise
o me al-based esponsi e a chi ec u es ha ac as molecula
machines.
5
Among he a ious possible applica ions, ulle ene
ecogni ion is one o he mos popula , as e idenced by he li e a u e
ega ding he cons uc ion o disc e e coo dina ion cages.
6
These
mo i s ely on he sel -assembly o he co esponding subuni s o
u nish a shape-pe sis en molecula cage wi h he app op ia e
ca i y size o hos a ulle ene and s abilize he inclusion complex
h ough mul iple a ac i e sup amolecula in e ac ions. In mos
cases, a s imulus capable o clea ing he me al–ligand bonds
disassembles he cage o elease he gues . Ano he simple
app oach could be he syn hesis o swi chable molecula weeze s
in which he coo dina ion (o decoo dina ion) e en igge s a
c ucial con o ma ional change o he ligand ha o ms (o dis up s)
an op imal ca i y o ulle ene ecogni ion. An app op ia ely unc-
ionalized 2,20-bipy idine (bpy)
7
should be able o wo k in his way,
aking ad an age o he p ope ies o bpy s uc u es as ligands and
he possibili y o syn–an i con o ma ional swi ching.
8
Some exam-
ples u ilizing his app oach wi h calix[5]a ene
9
o po phy in
10
cle s
ha e been epo ed. Howe e , hese examples exhibi ed some issues:
(1) he low s abili y o he coo dina ion complexes, (2) incomple e
e e sibili y o he sys em and (3) he lack o ON/OFF beha iou (i.e.,
he ulle ene ecogni ion is always ac i e o ‘‘ON’’, al hough i is
modula ed by he me al), a phenomenon ha we also obse ed in a
p e ious s udy using azobenzene-de i ed pho oswi chable hos s.
11
We en isaged he possibili y o designing a sup amolecula weeze
bea ing wo co annulene
12
moie ies whose con o ma ion would be
con olled by a chemical e ec o , allowing i o be ‘‘ u ned ON’’ o
ecognize ulle ene in a igid and well-de ined hos , and ‘‘ u ned
OFF’’ by sca enging he e ec o o gi e an ill-de ined hos wi hou a
sui able ca i y o in e ac wi h ulle enes (Scheme 1). Co annulene-
based hos s ha e been demons a ed o p o ide good pe o mance
in ulle ene ecogni ion in molecula weeze s,
13
molecula clips
wi h mul iple uni s,
14
molecula clips wi h an ac i e e he
15
and
polyme s
16
due o he excellen conca e–con ex complemen a i y
17
Scheme 1 Ope a ional p inciple o e e sible bis able molecula
weeze s o ulle ene ecogni ion con olled by a chemical effec o (E).
GIR MIOMeT, IU CINQUIMA/Quı
´mica Ino ga
´nica, Facul ad de Ciencias,
Uni e sidad de Valladolid, Valladolid, E47011, Spain.
E-mail: aul.ga c[email p o ec ed], celedonio.al[email p o ec ed]
†Elec onic supplemen a y in o ma ion (ESI) a ailable: De ailed syn he ic p o-
cedu es, ull cha ac e iza ion, in si u coo dina ion/decoo dina ion cyclic p ocess
desc ip ion and associa ion cons an measu emen s as well as compu a ional
calcula ion de ails. See DOI: 10.1039/d1cc03451k
‡These au ho s equally con ibu ed o his wo k.
Recei ed 28 h June 2021,
Accep ed 13 h Sep embe 2021
DOI: 10.1039/d1cc03451k
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be ween he wo species. In his wo k, o combine he in e es ing
p ope ies o eadily a ailable simple biden a e-chela ing bpy ligands
wi h he con enien cu ed opology o co annulene, we designed
ligands L1a and L2a (Scheme 2). Ou ligand design is based on he
ollowing equi emen s: (1) in he absence o he chemical e ec o ,
he sys em should lack a de ined ca i y o ulle ene ecogni ion (i.e.,
a noncoo dina ed o OFF s a e). We easoned ha a bipy idine
amewo k ligand could mee hese equi emen s, since ee bipy -
idines a e known o p e e he an i geome y due o s e ic hinde -
ance be ween he 3 and 30p o ons (ESI†).
8a
In his case, he absence
o a de ined ca i y o ulle ene ecogni ion should dis a ou he
o ma ion o a sup amolecula adduc . (2) The addi ion o an
e ec o should igge he o ma ion o a sui able ca i y o ulle ene
ecogni ion (i.e., an ON s a e). In his wo k we selec ed Cu(I)as he
e ec o , which coo dina es o he ligands o gi e he chela e
complexes Cu1a and Cu2a, enabling he selec ion o he syn
con o me . Bo h co annulene subuni s a e o ien ed on he same
side, c ea ing a p eo ganized ca i y eady o ulle ene ecogni ion.
Mo e impo an ly, his p ocess could be e e sible, as he wo
con o me s could be in e con e ed by sca enging he e ec o om
he ON s a e o elease he ee ligand, which would elax owa ds
he p e e ed an i con o ma ion, and he e o e dis up he inclusion
complex, comple ing he cycle. As a p oo o concep , we p esen
he e wo models: compound L1a, in which he co annulene uni s
a e di ec ly connec ed o he bpy hinge h ough a C–C bond a
posi ions 4 and 40, and compound L2a, which bea s an alkynyl
space g oup ha con e s a la ge dis ance be ween he wo
co annulene g oups. The esul ing ca i y in complex Cu2a would
be la ge han he one exhibi ed by complex Cu1a.This ea u e
migh impac i s abili y o ecognize ulle enes depending on he
o e all lexibili y and adap abili y o he hos . The p epa a ion o
weeze s L1a and L2a was ca ied ou by means o Suzuki–Miyau a
18
and Sonogashi a
19
C–C c oss coupling eac ions unde mic owa e
i adia ion, using 4,40-dib omo-2,20-bipy idine as he common s a -
ing ma e ial and ei he 1-b omoco annulene o 1-e hynylco a-
nnulene as he unc ionalized cu ed polycyclic a oma ic hyd oca -
bon. The subsequen complexes Cu1a and Cu2a a e easily ob ained
quan i a i ely by he addi ion o [Cu(NCMe)
4
]BF
4
in hep esenceo
1,2-bis(diphenylphosphino)e hane (dppe) (ESI†). The choice o his
seconda y ligand o comple e he coo dina ion sphe e o Cu(I)was
based on i s well-known s abili y, ease o emo al (see below) and
mild inge p in o
1
H-NMR s udies.
20
The inal compounds we e
ully cha ac e ized using 1D and 2D NMR measu emen s, UV-Vis
and emission spec oscopy, cyclic ol amme y and high- esolu ion
mass spec ome y (ESI†). The i s aspec we es ed was he
e e sibili y o he p ocess, i.e., a smoo h decoo dina ion/coo dina-
ion p o ocol. Me al sca enging in Cu(I) complexes is ypically
ca ied ou by he addi ion o an aqueous solu ion o ammonia o
excess o KCN o u nish he co esponding wa e -soluble com-
plexes, which can be sepa a ed om he esul ing ee bpy by
ex ac ion.
21
Howe e , his me hod equi es an addi ional pu i ica-
ion s ep, p ecluding ou aim o de eloping an in si u swi ching
p ocess. In ac , a emp s o apply hese p o ocols in si u (conduc ing
he eac ion in he NMR ube wi hou a pu i ica ion s ep) we e
unsuccess ul because (1) he p esence o pa amagne ic Cu(II) species
p e en ed NMR analysis and (2) a la ge excess o he eac an was
needed. To ci cum en hese issues, we de eloped an al e na i e
me hod by using he ligand dppe i sel as he sca enging agen ,
which allows in si u moni o ing o he whole cyclic ope a ion using
1
H-NMR. The addi ion o 1 equi . o dppe o complexes Cu1a o
Cu2a eleases ligand L1a o L2a o gi e he mo e s able homolep ic
complex [Cu(dppe)
2
]BF
4
as a byp oduc ha emains in solu ion. In
hecaseo complexCu1a, o ins ance,p o onsH
3
and H
6
( ed and
g een in Fig. 1) exhibi signi ican down ield shi s o 0.12 and
0.27 ppm upon ligand decoo dina ion, espec i ely, whe eas p o on
H
5
(blue in Fig. 1) is shi ed up ield by 0.16 ppm. The chemical shi s
o co annulene we e also impac ed upon coo dina ion. The s a ing
complex Cu1a can easily be es o ed by he addi ion o 0.5 equi . o
[Cu(NCMe)
4
]BF
4
, which is su icien o p oduce he e olep ic Cu1a by
ligand sc ambling, as e idenced by he changes in he chemical
shi s o he ele an bpy p o ons (H
3
,H
5
and H
6
)asshowninFig.1
(ESI†). This s aigh o wa d one-po app oach can be applied o a
la ge numbe o cycles, making i i ually in ini ely applicable.§As
no ed ea lie , L1a and L2a p e e he an i con o ma ion, whe eas
complexes Cu1a and Cu2a adop a syn geome y. Thus, ou simple
app oach allows excellen con ol o e he popula ion o bo h s a es.
Ano he ad an age o ou sys em is he chemical s abili y o
he in ol ed species, as hey do no exhibi in e con e sion
when allowed o s and a oom empe a u e o wo weeks.
Ha ing ha nessed he beha iou o hese sys ems in e ms o
con o ma ional con ol, we mo ed on o s udy hei capabili y
owa ds ulle ene ecogni ion. To do so, ulle enes C
60
and C
70
we e added o independen solu ions o ee ligands L1a and
Scheme 2 Chemical s uc u es o compounds L1a and L2a, whose
con o ma ional swi ching p ocess is go e ned by a Cu(I) effec o .
Fig. 1 In si u coo dina ion/decoo dina ion p ocess in bpy-de i ed mole-
cula weeze s along wi h s acked
1
H-NMR spec a o complex Cu1a
du ing h ee swi ching cycles in CD
2
Cl
2
a 298 K.
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L2a in CD
2
Cl
2
a 298 K. This sol en was chosen o e o he
mo e common a oma ic sol en s, such as oluene o chlo o-
benzene, o s abili y easons as he esul ing Cu(I) complexes
showed e idence o decoo dina ion a e 10 minu es in hose
sol en s. Gi en ha bo h ligands p e e he an i con o ma ion
and possess eedom o mo ion, nei he o med a ca i y
be ween hei wo co annulene uni s o hos a ulle ene (i.e.,
hey we e ill-de ined hos s); he e o e, no sup amolecula in e -
ac ion was obse ed and he chemical shi s did no change
(spec a a and b in Fig. 2). This esul is impo an , since i
clea ly indica es ha he sys em was in an OFF s a e as a esul
o he inabili y o he ee ligands o hos ulle ene. Complexes
Cu1a and Cu2a we e es ed using he same p o ocol. In hese
cases, ema kable changes in he chemical shi s o some o he
p o ons we e obse ed. As an example, spec a c and d in Fig. 2
highligh he changes in hyd ogens H
3
and H
6
o he couple
Cu1a/C
70
. P o on H
3
( ed in Fig. 2) was shi ed up ield by
0.073 ppm, whe eas p o on H
6
(g een in Fig. 2) exhibi ed a
down ield shi o 0.011 ppm. The signals o co annulene we e
also affec ed (Fig. S79–S90, ESI†). This beha iou clea ly
demons a es he exis ence o an associa ion be ween he
complexes and he ulle enes, as an e icien p eo ganized
ca i y has been buil be ween he wo co annulene subuni s,
which e ec i ely encloses he ulle enes due o he excellen
conca e–con ex su ace complemen a i y¶ (i.e., hey a e well-
de ined hos s) wi h an imposed syn con o ma ion by Cu(I). In
o he wo ds, he sys em is in he ON s a e. A e wa ds, addi-
ional cycles o decoo dina ion/coo dina ion we e ca ied ou ,
demons a ing he e e sibili y o he e ec o -induced ON/OFF
ansi ions o he molecula weeze s (Fig. 2) (ESI†). To
quan i y he ecogni ion capabili y o he epo ed hos s o
he ulle enes, we ca ied ou
1
H-NMR i a ions in CD
2
Cl
2
a
298 K, which ga e es ima ed associa ion cons an s (K
a
)o
(2.00 0.01) 10
3
M
1
and (4.99 0.01) 10
4
M
1
o
complex Cu1a wi h C
60
and C
70
, espec i ely (Fig. 3). Fo
compound Cu2a, he ob ained K
a
alues we e (1.15 0.01) 
10
3
M
1
o C
60
and (2.11 0.01) 10
4
M
1
o C
70
. The
epo ed alues we e i ed acco ding o a 1 :1 s oichiome y
model (ESI†). In ligh o hese esul s, wo conclusions we e
d awn: (1) he binding a ini y o he complexes owa ds C
70
a e
one o de o magni ude highe han hose owa ds C
60
,in
acco dance wi h he p e e ence o C
70
p e iously obse ed
o some co annulene-based molecula weeze s,
13a,c
and (2)
he longe e hynyl space in Cu2a does no d ama ically modi y
he ecogni ion capabili ies o he hos despi e he ac ha i s
ca i y is expec ed o be la ge , which could possibly weaken he
dispe sion and p–ps acking o ces. This demons a es he
adap abili y o his ai ly igid ecep o sugges ing ha he hos
and gues in e ac in an ex emely simila way in which ull-
e ene maximizes he app oach o he bpy e he . We a emp ed
o u he cha ac e ize he esul ing sup amolecula adduc s
using UV-Vis abso p ion expe imen s (Fig. S71, ESI†). Un o u-
na ely, he new cha ge- ans e band, which was expec ed o
appea a a ound l
abs
Z500 nm,
22
could no be obse ed. This
sugges s ha his band migh be e y weak, because (1) he
HOMO in he inclusion complex is me al-cen ed, unlike in he
ee ligand, whe e he e is a subs an ial con ibu ion a bo h
co annulene uni s, (Fig. S103, ESI†), (2) bpy o bi als a e no -
mally s abilized (i.e., lowe in ene gy) upon me al coo dina ion,
and (3) dispe sion o ces could play an impo an ole and be o
he same o de o highe han he cha ge– ans e in e ac ions,
as p e iously obse ed in P (II)-based molecula weeze s o a
simila na u e.
13a
In addi ion o hese ac o s, he associa ion
cons an s a e mode a e and he solubili y o he coo dina ion
complexes is low, and he e o e he concen a ion o he
inclusion complexes is expec ed o be e y low unde
he expe imen al condi ions. This e ec is also obse ed in
he emission spec a (Fig. S72, ESI†), in which he luo escence
quenching is almos negligible, and in he cyclic ol ammo-
g ams (Fig. S73 and S74, ESI†), whe e he ulle ene educ ion
po en ials a e no signi ican ly shi ed. Compu a ional model-
ling using DFT me hods was ca ied ou o ob ain u he
insigh in o he s uc u e o he sup amolecula adduc s in
solu ion (de ails in he ESI†). The geome ies o inclusion
complexes C
60
@Cu1a and C
60
@Cu2a we e op imized, and he
o me is depic ed in Fig. 3(c). The dis ances be ween he
cen oids o he co annulene agmen s a e 11.7 Å and 13.1 Å,
espec i ely. The p esence o he e hynyl space enla ges he
ca i y by ca. 1.4 Å. This ansla es in o a e age co annulene-
cen oid–C
60
dis ances o 3.4 Å o assembly C
60
@Cu1a and
Fig. 2 Mode o ope a ion o he Cu1a/L1a sys em and i s beha iou
owa ds C
70
as moni o ed using
1
H-NMR in CD
2
Cl
2
a 298 K.
Fig. 3 (a) Selec ed egion o he
1
H-NMR spec a o he sup amolecula
i a ion o Cu1a wi h C
60
in CD
2
Cl
2
a 298 K. (b) Plo o he changes in he
chemical shi (Dd)o H
3
agains [G]/[H], whe e Gis C
60
and His Cu1a. The
blue line co esponds o he nonlinea i ing o Dd o p o on H
3
o a 1 : 1
binding iso he m. (c) DFT-op imized geome y o assembly C
60
@Cu1a and
i s co esponding NCI plo as g adien isosu ace.
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3.6 Å o assembly C
60
@Cu2a, bo h o which a e sui able o
e icien a ac i e sup amolecula in e ac ions. This sugges s
ha complex Cu2a, despi e being a he igid, s ill possesses
su icien lexibili y o accommoda e a ulle ene molecule. This
ea u e is also e lec ed in he ma ginal di e ence in hei
expe imen al K
a
alues, calcula ed elec onic in e ac ion ene -
gies (0.6 kcal mol
1
) and hei simila NCI su aces, which
enclose a subs an ial po ion o he ou e ulle ene su ace
(Fig. 3c and ESI†).
In summa y, we ha e de eloped a s aigh o wa d syn hesis
o molecula weeze s based on bpy compounds bea ing con-
ca e co annulene agmen s whose ulle ene ecogni ion abil-
i ies can be modula ed by a chemical effec o h ough he
in si u o ma ion o e ahed al Cu(I) complexes. We ha e
demons a ed ha he p ocess is e e sible and ha he
me al-media ed swi ching can be easily accomplished. The
ecogni ion is comple ely deac i a ed in he OFF s a e, whe eas
good binding affini ies a e obse ed in he ON s a e, being one
o de o magni ude g ea e o C
70
e sus C
60
. Al hough he
sys em is qui e igid, i s ill exhibi s adap abili y, as demon-
s a ed by he binding affini ies obse ed o he wo molecula
weeze s wi h diffe en ca i y sizes, es ablishing a sub le bal-
ance be ween en opy-penalizing mild lexibili y and size
complemen a i y.
We hank he Spanish Minis y o Science, Inno a ion and
Uni e si ies (MCIU) o unding (p ojec numbe s PGC2018-
096880-A-I00, MCIU/AEI/FEDER, UE, PGC2018-099470-B-I00,
and MCIU/AEI/FEDER, UE). R. G.-R. acknowledges he Spanish
MINECO/AEI and he Eu opean Union (ESF) o a Ramo
´n
y Cajal con ac (RYC-2015-19035). H. B. acknowledges he
Al onso Ma ı
´n Escude o Founda ion o a pos doc o al
ellowship.
Con lic s o in e es
The e a e no con lic s o decla e.
No es and e e ences
§P o ided ha he byp oduc build-up does no in e e e wi h he
chemical p ocesses o he obse a ion o his phenomenon. This is no
he case a e 5 cycles.
¶ No e ha his ea u e is undamen al o ulle ene ecogni ion. To
demons a e he key ole o co annulene in ou ligand design, we
p epa ed py ene-based ligands (L1b and L2b) along wi h hei Cu(I)
complexes (Cu1b and Cu1b) and es ed hei ulle ene ecogni ion
abili y, which u nished nega i e esul s in all cases, e idencing ha
hei plana s uc u e is no sui able o molecula weeze s wi h his
design (ESI†).
1(a) S. E bas-Cakmak, D. A. Leigh, C. T. McTe nan and A. L.
Nussbaume , Chem. Re ., 2015, 115, 10081–10206; (b) M. Wei,
Y. Gao, X. Li and M. J. Se pe, Polym. Chem., 2017, 8, 127–143.
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