Sol en Con olled Gene a ion o Spin Ac i e Pola ons in Two-
Dimensional Ma e ial unde UV Ligh I adia ion
Gio gio Zoppella o, Mi osla Med ed, Ví ezsla H uby, Radek Zbo il, Michal O yepka,*and Pe Laza *
Ci e This: J. Am. Chem. Soc. 2024, 146, 15010−15018
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sı Suppo ing In o ma ion
ABSTRACT: Pola ons belong o a class o ex ensi ely s udied
quasipa icles ha ha e ound applica ions spanning di e se ields,
including cha ge anspo , colossal magne o esis ance, he mo-
elec ici y, (mul i) e oism, op oelec onics, and pho o ol aics. I is
no able, hough, ha hei in e ac ion wi h he local en i onmen
has been o e looked so a . We epo an unexpec ed phenomenon
o he sol en -induced gene a ion o pola onic spin ac i e s a es in
a wo-dimensional (2D) ma e ial luo og aphene unde UV ligh .
Fu he mo e, we p esen compelling e idence o he sol en -
speci ic na u e o his phenomenon. The gene a ion o spin-ac i e
s a es is obus in ace one, mode a e in benzene, and absen in
cyclohexane. Con inuous wa e X-band elec on pa amagne ic
esonance (EPR) spec oscopy expe imen s e ealed a massi e
inc ease in he EPR signal o luo og aphene dispe sed in ace one unde UV-ligh i adia ion, while he sys em did no show any
signi ican signal unde da k condi ions and wi hou he sol en . The pa e ns appea ed due o he gene a ion o ansien magne ic
pho oexci ed s a es o pola onic cha ac e , which encompassed he ne 1/2 spin momen de ec able by EPR. Ad anced ab ini io
calcula ions disclosed ha pola ons a e plausibly o med a adical si es in luo og aphene which in e ac s ongly wi h ace one
molecules in hei icini y. Addi ionally, we p esen a comp ehensi e scena io o mul iplica ion o pola onic spin ac i e species,
highligh ing he pi o al ole o he pho oinduced cha ge ans e om he sol en o he elec ophilic adical cen e s in
luo og aphene. We belie e ha he sol en - unable pola on o ma ion wi h he use o UV ligh and an easily accessible 2D
nanoma e ial opens up a wide ange o u u e applica ions, anging om molecula sensing o magne o-op ical de ices.
■INTRODUCTION
Pola ons a e composi e quasipa icles ha can o m in
pola izable ma e ials and ha e a p o ound impac on ma e ial
p ope ies and unc ionali ies. The e m pola on e e s o an
excess cha ge ca ie (elec on o hole) localized wi hin a
po en ial well gene a ed by a displacemen o su ounding ions.
In a quasipa icle pic u e, i is a quasipa icle consis ing o an
elec on o a hole d essed by a cloud o i ual phonons, which
ollows he pola on as i p opaga es h ough he c ys al. A
pola on may esul om he sepa a ion o exci ons, which a e
cha ge-neu al Coulomb-bound elec on−hole pai s. In his
con ex , pola ons and exci ons play a cen al ole in he
elec onic and op ical p ope ies o o ganic semiconduc ing
polyme s
1
and a e c ucial o unde s anding he ope a ion o
mode n o ganic op oelec onic de ices such as sola cells and
ligh -emi ing diodes.
2
Besides ha , pola ons we e ound o
s and behind he colossal magne o esis ance o manganese
pe o ski es,
3
e oelec ici y o lead halide pe o ski es,
4
su ace
eac i i y o TiO2,
5
o he Seebeck e ec in oxide-based
esis i e swi ching memo y,
6
o name jus he mos ele an
examples. A ecen e iew has summa ized almos 90 yea s o
esea ch in o pola on e ec s in ma e ials, comp ising an
eno mous amoun o da a.
7
Howe e , he physics o pola ons and o he quasipa icles
such as exci ons has been s udied mos ly in bulk c ys als and
on clean su aces in a acuum. In con as o bulk ma e ials,
expe imen al e idence o pola ons in wo-dimensional (2D)
ma e ials is a e.
8
Owing o his, ou undamen al unde -
s anding o quasipa icles a solid−gas and solid−liquid
in e aces has no ye been de eloped
9
despi e he ac ha
low dimensional nanoma e ials, including also 2D nanoma-
e ials like g aphene, ha e la ge su ace a ea exposed o he
ex e nal en i onmen , which mus a ec he ene ge ics and
beha io o pola ons in hese ma e ials. Op ical exci a ion nea
he in e ace can esul no only in he o ma ion o exci ons
bu also in he c ea ion o a weal h o o he quasipa icles such
as biexci ons, pola on pai s, and ions. Biexci ons a e c ea ed
om wo ee exci ons. A pola on pai is a Coulomb-bound
Recei ed: No embe 27, 2023
Re ised: Ap il 16, 2024
Accep ed: Ap il 17, 2024
Published: May 2, 2024
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pai o a nega i e and a posi i e pola on, si ua ed on opposi e
sides o he in e ace o on di e en molecules.
1,10
Pola on
pai s a e some imes also called cha ge- ans e exci ons. A
(nega i e) ion is an elec on−hole−elec on cha ged
quasipa icle ha ea u es a ne hal -in ege spin. The
unexpec ed ole o an in e ace is suppo ed by ecen s udies
which ha e e ealed a su p isingly s ong in e ac ion be ween
pola ons and su ace adso ba e molecules.
11,12
Namely,
pola ons signi ican ly modula ed adso p ion and dissocia ion
o wa e on he u ile (110) su ace,
11
and, in u n, CO
adso ba es we e able o al e he s abili y o pola ons in
u ile.
12
Coupling o pola ons o ex e nal molecules could be
c ucial in 2D ma e ials and nanoma e ials because hei
su aces a e exposed o in e ac ion wi h he en i onmen .
13
I is wo h no ing ha in chemis y, we can ind an analogue o
a pola on�a sol a ed elec on.
14
A sol a ed elec on is a
ca ie o nega i e cha ge in solu ion and is one o he mos
undamen al chemical eagen s. The in oduc ion o excess
elec ons s ongly pe u bs he s uc u e o molecules wi hin a
sc eening olume o he liquid solu ion in a manne simila o
how he pola on pe u bs he c ys alline la ice. The analogy
con inues as u he knowledge is being acqui ed ega ding he
p ope ies o sol a ed elec ons in homogeneous media;
howe e , much less is known abou hei beha io in
inhomogeneous media such as liquid/solid and liquid/ acuum
in e aces.
15
All o hese ac s mo i a ed us o s udy he
in e ac ion o a 2D ma e ial wi h a sol en .
We epo massi e gene a ion o spin ac i e s a es in a
luo og aphene (FG) ozen ma ix solu ion unde UV ligh
igge ed by speci ic sol en s, i.e., by he speci ic en i onmen
su ounding he pola ons in FG. We used con inuous wa e
(CW) X-band elec on pa amagne ic esonance (EPR) spec-
oscopy o de e mine he cha ac e o he gene a ed spin
ac i e species and o ollow he ime e olu ion unde a ious
condi ions. The expe imen al obse a ions we e elucida ed
wi h he help o heo e ical calcula ions based on he densi y
unc ional heo y (DFT) using bo h pe iodic and ini e-size
models including an explici sol en molecule. The ini e
models we e s udied by ime-dependen DFT (TD-DFT)
using he ωB97X-D and CAM-B3LYP unc ionals in
combina ion wi h he uni e sal implici sol a ion model
based on he solu e elec on densi y (SMD) in o de o
accoun o he dielec ic na u e o he sol en en i onmen .
The pe iodic model was used o s udy he pola on o ma ion
and elec on exci a ion in he p esence o sol en molecules.
Fo he la e , he TD-DFT and he G een unc ion (GW)
app oach combined wi h he Be he−Salpe e equa ion (BSE)
we e used.
16
This combined app oach allowed us o compu e
one-pa icle as well as wo-pa icle elec onic exci a ions in an
accu a e manne om he i s -p inciples, co ec ly cap u e
band alignmen a he molecule−su ace in e ace, and, a he
same ime, co ec ly accoun o he exci onic and local- ield
e ec s.
■RESULTS AND DISCUSSION
FG is a wide-gap 2D semiconduc o de i ed om g aphene,
17
which holds a g ea p omise o applica ions in high
pe o mance ma e ials such as ba e ies, dielec ics, o
biosenso s.
18
FG exhibi s unusually high exci on binding
ene gy o abou 2 eV owing o he s ongly bound F enkel
exci on.
19
We measu ed CW-EPR signals unde ligh
i adia ion a 3.8149 eV, which was below he op ical band
gap o p is ine FG (∼5.6 eV).
20
Figu e 1a shows he
expe imen al EPR signal (T= 90 K) o he nea FG powde
ma e ial ob ained om a comme cial sou ce (μm size shee s,
Sigma-Ald ich, g aphi e luo ina ed polyme , (CFx)n,x∼1.1)
eco ded unde da k condi ions, compa ed o he esonance
signal de ec ed du ing con inuous UV i adia ion (Figu e 1a,
uppe spec um). The de ailed chemical and spec oscopic
cha ac e iza ion o he comme cial FG ma e ial used
h oughou his s udy is gi en in he Suppo ing In o ma ion
(Figu es S1−S4). The obse ed EPR esonances shown in
Figu e 1a highligh he p esence o a complex pa e n ha
de eloped nea ly symme ically a ound g∼2.000. Such a
pa e n indica es he coexis ence o S= 1/2 and S= 1 s a es.
The spin con en was es ima ed as 10.03 ×1018 spin/g, using
CuSO4·5H2O spin S= 1/2 s anda d. Simila EPR ea u es and
compa able spin densi y (23.2 ×1018 spin/g) ha e been ea lie
obse ed o eme ge in a di e en comme cial ba ch o FG om
he same comme cial sou ce (g aphi e luo ina ed polyme ,
Sigma-Ald ich, CFx, wi h x∼1.1) and ha e been in e p e ed o
a ise om he p esence o spin ac i e de ec s in he 2D la ice
o FG. The e o e, he concen a ion o spin de ec s could
Figu e 1. X-band EPR spec a eco ded a T= 90 K: Panel (a) The spec um o FG powde unde da k condi ions (lowe spec um, 0.6 mW o
applied mic owa e powe ) compa ed o ha ob ained a e 10 min o in si u con inuous UV ligh i adia ion (uppe spec um, a 325 nm, 200
mW). Panel (b) The spec a o FG powde eshly dispe sed in (a) cyclohexane, (b) benzene, and (c) ace one, eco ded a e 10 min o in si u UV
i adia ion a 325 nm (o ange) and in da k condi ions (blue). Expe imen al condi ions: (a) 9.077 GHz equency, 1.6 mW mic owa e powe ; (b)
9.080 GHz equency, 1.0 mW mic owa e powe ; (c) 9.088 GHz equency, 0.6 mW mic owa e powe . The sol en s’ espec i e dielec ic
cons an s a e shown nex o he eco ded EPR aces (a−c).
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sligh ly a y in di e en FG ba ches, bu he p esence o
admix u e o S= 1/2 and S= 1 s a es in bulk solids appea s o
be a well- e ained p ope y o samples coming om he same
supplie . F om he expe imen al EPR esonances shown in
Figu e 1a, i was con i med ha in he powde o m he e we e
no signi ican di e ences be ween he EPR spec a o he FG
eco ded unde da k condi ions and unde UV ligh i adia ion.
When he FG powde was eshly dispe sed in cyclohexane
(∼1 mg/mL), and he EPR spec um o i s ozen ma ix
solu ion was eco ded a 90 K, an ex emely weak signal was
de ec ed due o a la ge diamagne ic dilu ion (Figu e 1b, EPR
ace a) compa ed o ha o he powde ma e ial in which clea
esonances we e seen. In si u i adia ion o he cyclohexane
ozen solu ion did no lead o he o ma ion o addi ional EPR
esonances o any inc ease in he EPR signal.
The EPR pa e ns changed d ama ically wi h FG eshly
dispe sed in benzene and ace one (Figu e 1b, EPR aces b,c)
(∼1 mg/mL) and eco ded unde UV-ligh i adia ion (10 min
i adia ion- ime inside he ca i y esona o be o e signal
acquisi ion). While nei he sys em showed any signi ican
EPR signals in he ozen ma ix suspensions (a T= 90 K) in
da k condi ions, upon i adia ion, a s ong asymme ic
esonance signal was de ec ed in he ace one solu ion and a
weake one was s ill clea ly disce nible in benzene. These
signals we e a ibu ed o he gene a ion o ansien spin
ac i e pho oexci ed s a es. In ace one, he e alua ed spin
concen a ion o FG eached a alue o 30.00 ×1018 spin/g,
which was abou 3 imes highe han o he ma e ial measu ed
unde da k condi ion. Upon hawing he samples and hen
ecooling down o 90 K, no le o e esidual pa amagne ic
signals we e de ec ed unde da k condi ions in bo h he
benzene and ace one solu ions, implying ha he pa amagne ic
ansien species did no emain in he FG solu ion wi hou
i adia ion. I mus be emphasized ha blank samples
con aining only he ace one o benzene sol en placed inside
he EPR ubes did no show he eme gence o any o such EPR
ea u es a e exposu e o UV ligh a 325 nm and a T= 90 K
o up o 30 min. Simila esul s we e ob ained o he oxygen-
ee solu ions. The e o e, all he ollowing expe imen s o he
FG sys em dispe sed ei he in benzene o ace one sol en s
we e conduc ed in oxygen- ee and ni ogen-sa u a ed
suspensions in o de o ob ain he bes possible spec al
esolu ions and o minimize pa amagne ic b oadening om
dissol ed oxygen on he de ec ed pho oexci ed spin species.
The pho oexci a ion dynamics was examined by in si u CW-
LEPR expe imen s using a ligh -o o ligh -on i adia ion
sequence a in e als o 30 s in he as scan mode wi hin he
ime window o 1800 s. To obse e i any spin elaxa ion
occu ed a 90 K, a ligh -o o ligh -on i adia ion sequence
was employed o he in si u signal de ec ion; 2.5 min unde
Figu e 2. (a) In si u ligh -induced X-band EPR spec a (LEPR) o FG powde (C1F1.1) eshly dispe sed in an oxygen ee benzene solu ion. The
sample was kep in a ni ogen sa u a ed a mosphe e. Expe imen al pa ame e s: 9.081 GHz equency, 1.0 mW mic owa e powe , 100 kHz
modula ion equency, 0.5 mT modula ion wid h, and 30 s acquisi ion ime o each sequen ial spec um. Signal acquisi ion sequence: 2.5 min
unde da k condi ions, ollowed by 7.5 min unde ligh i adia ion (a 325 nm), hen 20 min unde da k condi ions. (c) The co esponden 2D
LEPR plo o he spec a shown in panel (a). (b) LEPR spec a o FG powde (C1F1.1) eshly dispe sed in oxygen ee ace one solu ion.
Expe imen al pa ame e s: 9.075 GHz equency, 1.0 mW mic owa e powe , 100 kHz modula ion equency, 0.5 mT modula ion wid h, and 30 s
acquisi ion ime o each sequen ial spec um. Signal acquisi ion sequence: 2.5 min unde da k condi ions, ollowed by 7.5 min unde ligh
i adia ion (a 325 nm), hen 20 min unde da k condi ions. (d) The co esponden 2D LEPR plo o he spec a shown in panel (b).
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da k condi ions, ollowed by 7.5 min unde ligh i adia ion
and hen 20 min unde da k condi ions. The esul s ob ained
in hese dynamic ligh -induced EPR expe imen s a e shown in
Figu e 2a,c o he FG in benzene and in Figu e 2b,d o he
FG in he ace one solu ion. The eme gence o esonance
signals indica ed ha as soon as he UV ligh was swi ched on,
new pa amagne ic species we e clea ly gene a ed in he
sys ems. Speci ic EPR ea u es depended on he ype o
employed sol en . While in benzene, he weak and sligh ly
aniso opic signal s a ed o decay slowly as soon as he UV
ligh was cu o , he mos p ominen esonance signa u e o
FG dispe sed in ace one was mo e complex, and he EPR
signal did no decay wi hin he expe imen al ime window
employed (20 min da k condi ions). Mo eo e , he signal
eme ging unde pho oexci a ion was signi ican ly iche in
hype ine componen s (ei he om 1H o 19F, o om bo h)
and unde wen a signi ican eo ganiza ion du ing he ligh -on
o ligh -o ime window, indica ing ha in he FG-ace one
sys em, he e was a change in he spa ial con igu a ion o he
ace one molecules ha we e in e ac ing wi h he FG shee s.
We assume ha his change was no caused by he di usion o
ace one molecules because he solid-s a e sys em had limi ed
he mal mobili y a 90 K. P esumably, o a ional eedom o
he me hyl g oups o he ace one wi h espec o he FG plane
esul ed in he obse ed di e ences in he s eng h, ype, and
numbe o e ec i e hype ine componen s coupled o he
elec on spin momen when he ligh was cu o . Besides ha ,
he elec ic dipole-d i en eo ien a ion o ace one molecules
su ounding he pola ons may ha e played i s ole as well. In
bo h sys ems�FG in he benzene and ace one solu ion� he
spin sys ems can be in e p e ed as bound pola on s a es (h+/
e−), which a e cha ac e ized by he o ma ion o S= 1/2
species. F om he o e all shape o he esonance ansi ion
obse ed in he ozen ma ix, he gene a ion o popula ed
Figu e 3. (a) Abso p ion spec a o de ec ed FG in cyclohexane (CHX, g een line), benzene (BEN, blue line), and ace one (ACE, ed line)
solu ions compu ed wi hou (sho -dashed lines) and wi h (solid lines) an explici sol en molecule in he icini y o a adical de ec . Black e ical
dashed line deno es he wa eleng h o he applied UV ligh . G een, blue, and ed e ical dashed lines deno e he posi ions o he cha ge ans e
(CT, S0→S1) s a e in CHX, BEN, and ACE, espec i ely, (b) HOMO and lowes unoccupied molecula o bi al (i.e., SOMO) o he sol a ed
sys em in ace one, benzene, and cyclohexane ( om le o igh ) co obo a ing he CT cha ac e o ansi ions shown in (panel a). (c) P oposed
mechanism o he ini ial phase o he pho oac i a ion o he FG-sol en in e ace.
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iple s a es unde pho oexci a ion can be excluded a his
empe a u e. To u he gene alize ha he p esen ed
obse a ions hold also o FG sys ems ha ing smalle dimension
(nanome e size shee s), we p obed he exis ence o he
phenomenon in FG nanoshee s ob ained by sonica ion o he
comme cial FG ma e ial in ace one, in o de o p oduce small
FG agmen s wi hou inducing de luo ina ion p ocesses.
Syn he ic de ails and cha ac e iza ion o FG nano lakes a e
gi en in he Suppo ing In o ma ion. In pa icula , he EPR
spec um o small FG shee s eco ded unde ligh i adia ion
(Figu es S5 and S6) showed ha he ea u e o he
pho oexci ed e−/h+spin s a e (S= 1/2) o med in ace one
emained simila in shape and esonance posi ion o ha
obse ed in he la ge FG shee s eco ded in comme cial
sample (Ald ich). Howe e , in he small FG shee s, i was also
no ed ha in he pho oexci ed EPR spec a, a s onge
esonance signal a ound g∼2.00 eme ged, which was
associa ed wi h i mly localized spins on he ca bon backbone
o FG. This e ec was, he e o e, size dependen and indica ed
ha in he small FG shee s he e a e S= 1/2 si es ha ha e
limi ed coupling wi h he sol en molecules unde ligh
i adia ion. Howe e , he pho oexci ed LEPR spec a in bo h
la ge and small FG shee s emained consis en wi h he
o ma ion o small “Hols ein- ype” pola ons (localized
sys ems).
The subs an ial impac o a sol en on he beha io o ozen
FG solu ions unde UV-ligh adia ion obse ed in he EPR
expe imen s can be a ionalized in e ms o an in ica e
in e play o he exci ed s a es a he FG-sol en in e ace
a ising om a speci ic a angemen o elec onic le els o FG
de ec s and he sol en molecules. P is ine nonde ec i e FG
s a ed o abso b adia ion in he spec al egion below 220 nm
(∼5.6 eV),
20
and i s abso p ion was only mildly dependen on
he sol en pola i y (Figu e S7). Al hough he in e ac ion o
p is ine FG wi h an explici ace one molecule ga e ise o a
new abso p ion peak co esponding o he S0→S2(n(ACE)
→σ*(FG)) ansi ion, he exci a ion ene gy (∼6.1 eV, Figu e
S8) was also signi ican ly highe han ha o he applied
i adia ion (3.8 eV). I should be no ed ha he S0→S1
ansi ion in p is ine FG/ace one p edominan ly co esponds
o local n →π*exci a ion o ace one and his cha ac e o he
S0→S1 ansi ion was also co obo a ed by he ampli udes o
he BSE eigen ec o s ob ained om he BSE@GW0
calcula ion o he pe iodic FG model. Howe e , as al eady
men ioned, he eal samples o FG con ained di e en ypes o
de ec s including adical cen e s,
21
which may ha e played an
impo an ole in he FG pho oac i i y. Indeed, ou TD-DFT
calcula ions show ha he sole de ec i e FG exhibi ed a weak
abso p ion a ∼315 nm (3.9−4.0 eV) co esponding o he
σ(C−F) →SOMO ansi ion, which i ed he egion o
applied UV i adia ion (Figu e 3a). The posi ion and he
in ensi y o he peak depend only sligh ly on he sol en
pola i y, so his ansi ion can ha dly explain he dissimila
pe o mance o FG unde UV ligh in di e en en i onmen s.
Howe e , he compu a ions o models in ol ing an explici
sol en molecule in he icini y o he adical de ec e ealed
he eme gence o cha ge ans e (CT) exci ed s a es (Figu e
3b) wi h he ansi ion ene gies (and in ensi ies) being highly
dependen on he elec onic s uc u e o he sol en . While he
highes occupied molecula o bi al (HOMO) ene gies o
ace one and benzene made he CT s a e accessible ia in e nal
con e sion o he local exci a ion (LE) a he FG de ec in
hese sol en s, he low-lying σo bi als (e.g., HOMO−2) o
cyclohexane caused ha he CT s a e laid ene ge ically abo e
he LE s a e and hus was no eachable unde he condi ions
used in he expe imen s. The CT s a es o med in ace one and
benzene e en ually elaxed o he g ound s a e, bu he e y
low oscilla o s eng hs (Figu e 3a), especially in he case o
ace one, sugges ha he adia i e de-exci a ion was no
p obable, and he non adia i e pa hways we e hampe ed in he
ozen s a e by low empe a u e and la ice con inemen ,
dissimila o liquid solu ions. Al hough he p oposed
mechanism clea ly dis inguishes be ween he pho oac i e and
ine sol en s, i should be unde lined ha i only desc ibes he
i s phase o he FG pho oac i a ion and does no explain he
p oli e a ion o spin-ac i e species. In ac , he elec on ans e
om ace one o SOMO localized in he FG de ec si e leads o
he o ma ion o a spin-inac i e excess-elec on si e. Howe e ,
as e ealed by ou DFT calcula ions, in he icini y o such an
anionic si e, some C−F become suscep ible owa d he elease
o F−anions (e.g., he C−F bond leng hs nex o a de ec
inc eased om 1.39 o1.45 Å upon he o ma ion o an anion).
The ac i a ion ba ie o such a p ocess was es ima ed o ca.
13.3 kcal/mol (Figu e S9). While he elease o a neighbo ing
F−p ese es he closed-shell cha ac e o he sys em (pa h A in
Figu e S10), i can be an icipa ed ha o he si es (e.g.,
w inkles, buckles, and edges) can be p one o he C−F bond
clea age as well in eal FG samples, and such clea age could
lead o c ea ion o new spin-ac i e si es. Al hough he ho ough
explo a ion o such p ocesses would be compu a ionally highly
demanding, as an example, we in es iga ed an FG model
con aining a buckle nea by he anionic si e (Figu e S10). We
ound ha o ini e-size models he iple s uc u e (B) was
only by 0.29 eV ene ge ically less a o able han A. Acco ding
o pe iodic model calcula ions, he s uc u e B was e en mo e
s able han A (by ca. 0.31 eV, Figu e S11). Le us no e ha he
di e ences be ween he ini e-size and pe iodic s uc u es can
a ise om he la ge lexibili y o he o me . Ou calcula ions
hus indica e ha he o ma ion o sepa a ed spin species
(appea ing as S= 1/2 species o mo e dis an de ec s) migh
be an ene ge ically easible p ocess. This could explain he
mul iplica ion o spin-ac i e species as well as hei backbone
na u e, as obse ed in EPR expe imen s. The gene a ion o
h ee spin-ac i e species (one on an ace one molecule and wo
on he FG backbone) om a single adical si e is also in line
wi h he obse ed app oxima ely h ee imes highe spin
concen a ion in i adia ed FG in ace one compa ed o ha
measu ed unde da k condi ions. In addi ion, i can be
an icipa ed ha he pola on pai s o med a he in e ace may
ha e spli due o sc eening o he ex a cha ge by he sol en .
Such spli ing may ha e allowed he holes o mig a e in o he
sol en bulk (and/o o he FG-sol en in e ace), especially in
highly pola ace one, which indeed ea u ed much longe
li e imes o adical species han did he FG-benzene sys em.
Whe he o no he dissocia ion o an exci on o an elec on−
hole pai ac oss he ma e ial in e ace esul s in ee cha ges
depends s ongly on he dielec ic cons an s o molecula
sol en s.
22
The dielec ic cons an o ace one (ε= 20.70) is
much highe han ha o benzene (2.27) and hexane (2.02).
The spli ing o pola on pai s in o ee cha ges could hus
explain he s ong mul iplica ion o pola on s a es in FG/
ace one unde con inuous UV i adia ion.
The p esence o pola on s a es in he FG ace one sys em
was co obo a ed by u he EPR expe imen s. S a ing om
he silen EPR signal obse ed unde da k condi ions (Figu e
4, ace a), upon in si u i adia ion o 3 min ollowed by
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immedia ely cu ing o he ligh , spec um b was eco ded
wi hin he selec ed 2 min o acquisi ion ime (using 0.5 mT
modula ion wid h). The signal can be simula ed wi h S= 1/2
o he Zeeman e m (ge- enso (x,y,z) = 2.0013, 2.0013,
2.0013) plus he con ibu ion om he hype ine in e ac ions
(gβeBSz+Σ(A0)SzIz) wi h h ee H a oms associa ed wi h he
ace one molecule (1:3:3:1 pa e n, A- enso o 1H = 2.25,
2.25, 2.25 mT). The EPR spec um simula ion o he eco ded
pa e n is gi en in he Suppo ing In o ma ion (Figu e S12).
A e i adia ion o 7.5 min ollowed by 10 min unde da k
condi ions, spec um b con e ed o ace c, which was la gely
asymme ic and much iche in hype ine componen s.
Spec um c con e ed o spec um d upon hawing o oom
empe a u e and ecooling down o 90 K unde da k
condi ions. No de ec able esidual o s able spins emained
in he FG sys em a e hawing.
In o de o unde s and i hese esonance componen s
esul ed solely om 1H nuclei om he ace one molecules o
whe he 19F nuclei om FG con ibu ed o he eco ded signal,
we pe o med he same expe imen s using deu e a ed ace one
sol en (ace one-d6) unde iden ical expe imen al condi ions
excep o he smalle modula ion wid h o 0.05 mT used o
eco d he esonance signal (Figu e 4, ace e). A clea sep e
was obse ed, co esponding o spin densi y esiding on six
luo ine nuclei (ge- enso (x,y,z) = 2.0005, 2.0005, 2.0005; A-
enso o 19F = 0.34, 0.34, 0.34 mT) o e lapped o a second
b oad esonance componen . The e o e, he cen al (de i a-
i e) signal de ec ed in he spec um (c) a ound g= 2.0005
a ose om he e−couple coun e pa o he pola on pai
sys em ha was loca ed on he FG backbone. The EPR
spec um simula ion o he eco ded pa e n and addi ional
LEPR spec a using an in si u acquisi ion sequence such as
ligh -o , ligh -on, and ligh -o (2.5, 7.5, and 10 min,
espec i ely) is gi en in he Suppo ing In o ma ion (Figu e
S13, Figu e S14). The side signal was gene a ed by a hole
loca ed on he ace one molecule in e ac ing wi h FG. The ac
ha he EPR signal in he ace one-d6sys em was well esol ed
in he 19F hype ine componen s indica es ha he elec on−
hole pai s we e s ongly bound oge he by he Coulomb
in e ac ion. The s ong Coulomb in e ac ion occu ed due o
he low sc eening cha ac e is ic o FG
19,23
and o wo-
dimensional ma e ials in gene al.
24
Thus, he magne ically
ac i e pho oexci ed s a e can be conside ed a quasipa icle
sys em, encompassing ne 1/2 spin momen . This in e p e a-
ion was co obo a ed by addi ional pe iodic DFT calcula ions
o he FG adical/ace one sys em. When an elec on was
added o he sys em, he nega i e cha ge s ongly localized a
he de ec si e (Figu e 4b). The a oms in he icini y o he
adical si e elaxed hei posi ions; i.e., he pola on was o med.
The pola on was as small as wo adjacen ca bon pzo bi als o
he F adical de ec . The a omic displacemen s we e highly
localized, and only he i s shell o F a oms a ound he pola on
cen e exhibi ed non-negligible dis o ions om hei ini ial
posi ions. The bond be ween he adical and h ee adjacen
ca bon a oms is sho ened by 0.05 Å, while he C−F dis ance
om he adical o he nea es F a om is inc eased by 0.08 Å.
The C−F bond leng h o hese h ee F a oms is inc eased by
0.07 Å due o he p esence o he pola on. The elaxa ion
ene gy due o pola on o ma ion was 0.634 eV. These
signa u es a e inge p in s o a Hols ein- ype pola on. The
ace one molecule in e ac ed wi h he pola on since he cha ge
densi y accumula ed a he in e ace be ween he molecule and
he adical de ec (Figu e 4b and Figu e S14) and p omo ed
pola on o ma ion, as he elaxa ion ene gy was 0.42 eV
wi hou ace one. No ably, when an elec on was ex ac ed om
he sys em, o ming a hole, he esul ing posi i e cha ge
became localized on he ace one molecule (Figu e S16).
P esumably, he ace one ozen ma ix su ounding FG may
ha e se ed as a hole anspo laye ,
25
allowing u he
exci a ion o elec ons in o FG and o ma ion o o he
quasipa icles such as ions. Kwon e al. demons a ed ha
when a pola on was localized wi h he exci on a he chemically
enginee ed cha ge de ec cen e s, b igh ly luo escen ions
we e p oduced.
26
■CONCLUSIONS
In conclusion, ou indings unde sco e he c ucial ole o he
sol en en i onmen in ini ia ing he signi ican gene a ion o
spin-ac i e s a es in he 2D g aphene de i a i e upon UV
i adia ion. Fo FG eshly dispe sed in benzene and ace one,
he EPR spec a changed d ama ically upon i adia ion; a e y
s ong asymme ic esonance signal was de ec ed in ace one
solu ion and a weak one bu s ill disce nible in benzene. The
p esence o he sol en was c ucial, as he e was no di e ence
be ween he EPR spec a in he da k and unde UV ligh o
he nea FG powde and o he blank samples con aining only
he ace one o he benzene sol en . As o he ace one sol en ,
he dynamics o he pho oexci a ion p ocesses showed
signi ican eo ganiza ion du ing he ligh -on o ligh -o ime
window due o changes in he spa ial con igu a ion o he
Figu e 4. (a) X-band EPR spec a o FG powde eshly dispe sed in
oxygen- ee ace one sol en and eco ded a T= 90 K unde da k
condi ions ( ace a), FG/ace one eco ded a e 3 min unde UV
i adia ion (@325 nm) ( ace b), FG/ace one eco ded a e 7.5 min
unde UV i adia ion ollowed by 10 min unde da k condi ions ( ace
c), FG/ace one a e UV i adia ion (7.5 min), hawed a oom
empe a u e and inally cooled back unde da k condi ions a T= 90
K ( ace d), and FG/deu e a ed ace one (ace one-d6) eco ded a T=
90 K a e 7.5 min unde UV i adia ion ollowed by 10 min unde
da k condi ions ( ace e, bo om spec um). (b) FG adical/ace one
sys em; he cha ge densi y di e ence due o an ex a elec on (w. . .
he cha ge densi y o he neu al sys em).
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15015
ace one molecules in e ac ing wi h he luo og aphene shee s.
The spin sys ems gene a ed by UV ligh can be in e p e ed as
bound pola on pai s (h+, sol en /e−, FG shee s), which has
been suppo ed by heo e ical calcula ions showing pola on
o ma ion in he adical de ec s o he FG p omo ed by
ace one. Ou wo k demons a es ha besides he well-
es ablished a ge ed enginee ing o de ec s in ma e ials aimed
a p oducing pola ons, ions, qubi s, e c., addi ional e o
should be de o ed o unde s anding hei mu ual in e ac ions
wi h he en i onmen , which could be enhanced by inding he
bes sol en (o sol en mix u e) o he desi ed p ocess. The
obse a ion o he sol en unable pola on o ma ion in he
ligh weigh and he easily accessible nanoma e ial opens up a
wide ange o applica ions including, e.g., no only molecula
sensing o magne o-op ical de ices bu also hole- anspo
laye s in pe o ski e sola cells and N−V de ec s in diamond,
which holds po en ial o qubi ealiza ion in quan um
compu ing.
■EXPERIMENTAL SECTION
The pe iodic DFT calcula ions we e pe o med using he p ojec o -
augmen ed wa e me hod implemen ed in he Vienna ab ini io
simula ion package (VASP) sui e.
27
The po en ials used in he p esen
wo k we e he la es GW po en ials dis ibu ed wi h VASP ( asp.6.3).
The p imi i e cell o FG was c ea ed by adop ing he chai
con o ma ion
28
and he in-plane la ice pa ame e ao 1.29 Å.
29
A
supe cell app oach was used o model he su ace o FG including he
adical de ec ( luo ine acancy); we adop ed he 6 ×6 supe cell (72
ca bon and 72 luo ine a oms) and modeled he adical de ec by
emo ing single luo ine a om ollowed by s uc u al elaxa ion. The
ene gy cu o o he plane-wa e expansion was se o 400 eV, and he
3×3×1k-poin g id was used o sample he B illouin zone o he
supe cell. The geome y o he adical de ec and o he physiso bed
ace one was a ained by using he op imized an de Waals DFT
unc ional (op B86b- dW),
30
which included nonlocal co ela ion
e ec s and p o ided e y accu a e esul s o a ious g aphene−
molecule complexes.
31
The pe iodically epea ed shee s we e
sepa a ed by a leas 10 Å o acuum. The di e en ial cha ge
densi ies we e plo ed using he VESTA sui e.
32
The GW calcula ion
was pe o med on op o he Kohn−Sham o bi als. The G een’s
unc ion was i e a ed sel -consis en ly while keeping he sc eened
po en ial W a i s ini ial shape ( his me hod is usually deno ed as
GW0). In GW calcula ion, we kep he 3 ×3×1k-poin g id
(co esponding o he 9 ×9×1k-poin g id in he uni cell) and he
ene gy cu o o 400 eV. We added a la ge numbe o emp y bands so
GW calcula ions we e pe o med using a leas 1500 unoccupied
bands, which is essen ial o hei con e gency.
19
The Be he−Salpe e
equa ion was sol ed on op o he GW0calcula ion using he same se
o compu a ional pa ame e s. I should be no ed ha a GW/BSE
calcula ion may need a e y dense k-poin mesh and high ene gy
cu o o ully con e ge,
33
which is ex emely compu a ionally
demanding o he la ge supe cell used in his wo k. Based on
p e ious s udy o FG
19
and ou es s o he ace one molecule, we
es ima e ha ou calcula ion is con e ged o wi hin a ew meV. In
addi ion, he TD-DFT was used o he calcula ions in ol ing he
la ge 6 ×6 supe cell. The es calcula ion showed ha he TF-DFT
ep oduced well bo h he FG op ical and elec onic band gaps when
he hyb id unc ional PBE0
34
was used as he ke nel (Figu e S17) and
hus he TD-DFT could be used o la ge -scale calcula ions.
The s uc u es o ini e size model sys ems we e op imized
employing he ωB97X-D unc ional
35
in combina ion wi h he 6-
31++G(d,p) a omic basis se .
36
In all cases, ib a ional analysis was
pe o med and he absence o imagina y equencies was checked o
con i m he cha ac e o he s a iona y poin s on he po en ial ene gy
su ace. Bulk sol en e ec s (apa om an explici sol en molecule)
we e accoun ed o by using implici sol a ion model based on densi y
(SMD).
37
Elec onic ansi ions we e explo ed using he TD-DFT
employing he CAM-B3LYP unc ional
38
wi h he same basis se . All
calcula ions we e pe o med using he Gaussian16 p og am.
39
De ailed chemical and spec oscopic cha ac e iza ion o he
comme cial FG ma e ial employed in his s udy is gi en in he
Suppo ing In o ma ion (g aphi e luo ina ed polyme , Sigma-Ald ich,
CAS numbe : 51311-17-2, linea o mula: (CFx)n,x∼1.1).
Con inuous wa e elec on pa amagne ic esonance spec a and ligh
induced spec a we e eco ded on a JEOL JES-X-320 spec ome e
(JEOL, Tokyo, Japan) ope a ing a he X-band equency (∼9.0−9.1
GHz) equipped wi h a a iable- empe a u e con olle (He, N2) ES-
CT470 appa a us. Highly pu e qua z ubes we e employed (Sup asil,
Wilmad, ≤0.5 OD) as sample holde s, and accu acy on he
expe imen ally de e mined g- alues we e ob ained by using Mn(II)/
MgO s anda d (JEOL s anda d). The ca i y quali y ac o (Q) was
kep abo e 6500 in all measu emen s. Filling ac o s we e kep he
same (200 μL) in all expe imen s. The EPR and LEPR spec a we e
acqui ed unde non powe sa u a ing condi ions, upon ca e ul con ol
o he applied mic owa e powe du ing signal acquisi ion. In si u ligh
exci a ion EPR expe imen s (CW-LEPR) we e pe o med by
deploying a HeCd lase sou ce ope a ing a 325 nm (max ou pu
powe o 200 mW) om Kimmon Koha Co. L d. (Tokyo, Japan).
The UV-ligh was shined di ec ly on o he sample, kep ozen inside
he ca i y EPR esona o , and by using a dedica ed op ical ibe i ed
h ough he esona o op ical window. The in si u moni o ing o he
UV ligh -o o ligh -on p ocess was ope a ed by a ligh on−o shu e
mechanism.
■ASSOCIATED CONTENT
*
sı Suppo 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/jacs.3c13296.
The expe imen al aw da a (ASCII o ma ) associa ed o
he X-band EPR spec a gi en in Figu es 1,2, and 4a,
main ex ; chemical and spec oscopic cha ac e iza ion
o comme cial as well as o newly syn hesized FG
nanoshee s (Fou ie ans o m in a ed, XPS, XRD
cha ac e iza ion, and SEM images o he p is ine and
small FG shee s); esul s o DFT modeling (xyz
coo dina es o DFT calcula ions using local models;
and s uc u es and ou pu iles o pe iodic DFT
models) (ZIP)
Chemical and spec oscopic cha ac e iza ion o com-
me cial as well as o newly syn hesized FG nanoshee s;
aw da a om EPR expe imen s; Fou ie ans o m
in a ed, XPS, XRD cha ac e iza ion, and SEM images o
he p is ine and small FG shee s; esul s o DFT
modeling; xyz coo dina es o DFT calcula ions using
local models; and s uc u es and ou pu iles o pe iodic
DFT models (PDF)
■AUTHOR INFORMATION
Co esponding Au ho s
Michal O yepka −Regional Cen e o Ad anced Technologies
and Ma e ials, The Czech Ad anced Technology and
Resea ch Ins i u e (CATRIN), PalackyUni e si y Olomouc,
Olomouc 779 00, Czech Republic; IT4Inno a ions, VSB−
Technical Uni e si y o Os a a, Os a a-Po uba 708 00,
Czech Republic; o cid.o g/0000-0002-1066-5677;
Email: [email p o ec ed]
Pe Laza −Regional Cen e o Ad anced Technologies and
Ma e ials, The Czech Ad anced Technology and Resea ch
Ins i u e (CATRIN), PalackyUni e si y Olomouc, Olomouc
779 00, Czech Republic; o cid.o g/0000-0002-7312-
3656; Email: [email p o ec ed]
Jou nal o he Ame ican Chemical Socie y pubs.acs.o g/JACS A icle
h ps://doi.o g/10.1021/jacs.3c13296
J. Am. Chem. Soc. 2024, 146, 15010−15018
15016
Au ho s
Gio gio Zoppella o −Regional Cen e o Ad anced
Technologies and Ma e ials, The Czech Ad anced
Technology and Resea ch Ins i u e (CATRIN), Palacky
Uni e si y Olomouc, Olomouc 779 00, Czech Republic;
Nano echnology Cen e, Cen e o Ene gy and
En i onmen al Technologies (CEET), VSB�Technical
Uni e si y o Os a a, Os a a-Po uba 708 00, Czech
Republic
Mi osla Med ed

−Regional Cen e o Ad anced
Technologies and Ma e ials, The Czech Ad anced
Technology and Resea ch Ins i u e (CATRIN), Palacky
Uni e si y Olomouc, Olomouc 779 00, Czech Republic;
Depa men o Chemis y, Facul y o Na u al Sciences, Ma ej
Bel Uni e si y, BanskáBys ica 974 01, Slo ak Republic;
o cid.o g/0000-0001-8599-1031
Ví ezsla H uby−Regional Cen e o Ad anced Technologies
and Ma e ials, The Czech Ad anced Technology and
Resea ch Ins i u e (CATRIN), PalackyUni e si y Olomouc,
Olomouc 779 00, Czech Republic; Depa men o Physical
Chemis y, Facul y o Science, PalackyUni e si y Olomouc,
Olomouc 771 46, Czech Republic; o cid.o g/0000-0001-
8802-4290
Radek Zbo 
il −Regional Cen e o Ad anced Technologies
and Ma e ials, The Czech Ad anced Technology and
Resea ch Ins i u e (CATRIN), PalackyUni e si y Olomouc,
Olomouc 779 00, Czech Republic; Nano echnology Cen e,
Cen e o Ene gy and En i onmen al Technologies (CEET),
VSB�Technical Uni e si y o Os a a, Os a a-Po uba 708
00, Czech Republic; o cid.o g/0000-0002-3147-2196
Comple e con ac in o ma ion is a ailable a :
h ps://pubs.acs.o g/10.1021/jacs.3c13296
Au ho Con ibu ions
The manusc ip was w i en h ough con ibu ions o all
au ho s.
Funding
The wo k was suppo ed by he Czech Science Founda ion
(GACR), p ojec no. GA22-33284S.
No es
The au ho s decla e no compe ing inancial in e es .
■ACKNOWLEDGMENTS
The wo k was suppo ed by he Czech Science Founda ion
(GACR), p ojec no. GA22-33284S. We hank Vik o ie
Vícho á o X- ay di ac ion (XRD) measu emen , Ma in
Pe o X- ay pho oelec on spec oscopy (XPS) measu e-
men s, and E ini Ioannou o scanning elec on mic oscopy
(SEM) imaging. R.Z. acknowledges suppo om he Eu o-
pean Union’s Ho izon 2020 p ojec SAN4Fuel (g an no.
HORIZON-WIDERA-2021-ACCESS-03-01:101079384). We
acknowledge he suppo om ERDF/ESF p ojec TECHS-
CALE (no. CZ.02.01.01/00/22_008/0004587), he COST
Ac ion CA21101, and he Eu opean Union unde he
REFRESH�Resea ch Excellence o Region Sus ainabili y
and High- ech Indus ies p ojec numbe CZ.10.03.01/00/
22_003/0000048 ia he Ope a ional P og amme Jus
T ansi ion. This wo k was suppo ed by he Minis y o
Educa ion, You h and Spo s o he Czech Republic h ough
he e-INFRA CZ (ID: 90254).
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