The excited-state intramolecular proton transfer properties of three imine-linked two-dimensional porous organic polymers

Article abstract of DOI:10.1039/c7tc00123a

We report the synthesis and excited-state intramolecular proton transfer (ESIPT) properties of three tris(N-salicylideneaniline)-based (TSA) imine-linked porous organic polymers (POPs) containing C₃-symmetric 1,3,5-Triarylbenzene (TAB),-Tristyr

Full text of DOI:10.1039/c7tc00123a

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ISSN 2050-7526
PAPER
~
Nguyên T. K. Thanh, Xiaodi Su et al.
Fine-tuning of gold nanorod dimensions and plasmonic properties using
the Hofmeister effects
rsc.li/materials-c

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DOI: 10.1039/C7TC00123A
JournalꢀNameꢀ
COMMUNICATIONꢀ
ꢀ
TheꢀExcited-StateꢀIntramolecularꢀProtonꢀTransferꢀPropertiesꢀofꢀ
ThreeꢀImine-LinkedꢀTwo-DimensionalꢀPorousꢀOrganicꢀPolymersꢀꢀ
Receivedꢀ00thꢀJanuaryꢀ20xx,ꢀ
Acceptedꢀ00thꢀJanuaryꢀ20xxꢀ
PradeepkumarꢀJagadesan,ꢀGraceꢀEder,ꢀPsarasꢀL.ꢀMcGrier*ꢀ
DOI:ꢀ10.1039/x0xx00000xꢀ
www.rsc.org/ꢀ
Weꢀreportꢀtheꢀsynthesisꢀandꢀexcited-stateꢀintramolecularꢀprotonꢀ
transferꢀ (ESIPT)ꢀ propertiesꢀ ofꢀ threeꢀ tris(N-salicylideneaniline)-
basedꢀ (TSA)ꢀ imine-linkedꢀ porousꢀ organicꢀ polymersꢀ (POPs)ꢀ
ꢀ
containingꢀ
C
3
-symmetricꢀ 1,3,5-triarylbenzeneꢀ (TAB),ꢀ
-
tristyrylbenzeneꢀ (TSB),ꢀ andꢀ -tris(arylethynyl)benzeneꢀ (TAE)ꢀ
monomerꢀ units.ꢀ Theꢀ TSA-POPsꢀ areꢀ fluorescentꢀ inꢀ theꢀ solid-stateꢀ
2
+
2+
andꢀresponsiveꢀtoꢀCu ꢀandꢀPd .ꢀꢀꢀꢀ
[1]
Excited-stateꢀ intramolecularꢀ protonꢀ transferꢀ (ESIPT) ꢀ isꢀ aꢀ
phototautomerizationꢀthatꢀoccursꢀwhenꢀaꢀchromophoreꢀcontainingꢀ
2
anꢀintramolecularꢀprotonꢀdonorꢀ(-OH,ꢀ-NH )ꢀandꢀprotonꢀacceptorꢀ(-
C=O,ꢀ-C=N-)ꢀareꢀinꢀcloseꢀproximity.ꢀAꢀkeyꢀfeatureꢀofꢀESIPTꢀisꢀaꢀlargeꢀ
Stokesꢀ shiftedꢀ emissionꢀ withoutꢀ self-absorption,ꢀ whichꢀ emanatesꢀ
fromꢀ aꢀ rapidꢀ photoinducedꢀ enol-ketoꢀ tautomerizationꢀ processꢀ
(
Schemeꢀ1).ꢀThisꢀuniqueꢀfeatureꢀmakesꢀchromophoresꢀthatꢀexhibitꢀ
[2]
ESIPTꢀ potentiallyꢀ usefulꢀ forꢀ theꢀ constructionꢀ ofꢀ laserꢀ dyes, ꢀ
[3]
[4]
photostabilizers, ꢀ chemicalꢀ sensors, ꢀ andꢀ optoelectronicꢀ
Schemeꢀ 1ꢀ Schematicꢀ representationꢀ ofꢀ theꢀ ESIPTꢀ enol-ketoꢀ
tautomerizationꢀprocessꢀforꢀtheꢀTSA-BasedꢀPOPs.ꢀ
[5]
devices. ꢀAlthoughꢀtheꢀESIPTꢀpropertiesꢀofꢀvariousꢀsingle-moleculeꢀ
[6]
[7]
systems ꢀ andꢀ one-dimensionalꢀ (1D) ꢀ polymersꢀ haveꢀ beenꢀ
[8]
[20]ꢀ
evaluated,ꢀtwo-dimensionalꢀ(2D) ꢀpolymericꢀmaterialsꢀthatꢀexhibitꢀ frameworksꢀ (PPFs)
haveꢀ beenꢀ synthesizedꢀ employingꢀ variousꢀ
ESIPTꢀ areꢀ extremelyꢀ rare.ꢀ Recently,ꢀ weꢀ haveꢀ demonstratedꢀ thatꢀ fluorescentꢀ π-conjugatedꢀ units,ꢀ onlyꢀ aꢀ limitedꢀ numberꢀ exhibitꢀ
tris(N-salicylideneaniline)ꢀ (TSA)ꢀ chromophoresꢀ containingꢀ luminescence.ꢀ Theꢀ absenceꢀ ofꢀ luminescenceꢀ inꢀ theseꢀ systemsꢀ isꢀ
preformedꢀ C=NŸŸŸH-Oꢀ bondsꢀ exhibitꢀ enhancedꢀ luminescentꢀ mostlyꢀ attributedꢀ toꢀ aggregationꢀ causedꢀ quenchingꢀ (ACQ),ꢀ whichꢀ
propertiesꢀinꢀtheꢀsolid-stateꢀdueꢀtoꢀtheirꢀabilityꢀtoꢀundergoꢀefficientꢀ oftenꢀ occursꢀ dueꢀ toꢀ theꢀ strongꢀ π-πꢀ interactionsꢀ betweenꢀ theꢀ
[9]
ESIPTꢀ toꢀ formꢀ theꢀ ketoꢀ tautomer. ꢀ However,ꢀ utilizingꢀ TSAꢀ adjacentꢀ layersꢀ ofꢀ theꢀ material.ꢀ However,ꢀ aꢀ majorityꢀ ofꢀ theꢀ POPsꢀ
chromophoresꢀ toꢀ constructꢀ imine-linkedꢀ 2Dꢀ porousꢀ organicꢀ thatꢀ exhibitꢀ fluorescenceꢀ inꢀ theꢀ solid-stateꢀ isꢀ creditedꢀ toꢀ anꢀ
[10]
[21]
polymersꢀ(POPs) ꢀthatꢀcanꢀundergoꢀESIPTꢀhasꢀnotꢀbeenꢀreportedꢀ aggregation-inducedꢀ emissionꢀ (AIE)ꢀ mechanism. ꢀ AIEꢀ typicallyꢀ
toꢀdate.ꢀ reliesꢀonꢀtheꢀrestrictedꢀintramolecularꢀrotationꢀorꢀmotionꢀofꢀtheꢀπ-
POPsꢀ areꢀ aꢀ uniqueꢀ classꢀ ofꢀ amorphousꢀ porousꢀ polymersꢀ thatꢀ conjugatedꢀ unitsꢀ toꢀ produceꢀ aꢀ luminescenceꢀ response.ꢀ Asꢀ aꢀ
ꢀ
[11]
haveꢀ beenꢀ utilizedꢀ forꢀ applicationsꢀ relatedꢀ toꢀ gasꢀ storage,
ꢀ
consequence,ꢀ onlyꢀ aꢀ handfulꢀ ofꢀ π-conjugatedꢀ monomersꢀ canꢀ beꢀ
[12]
[13]
[14]
separations, ꢀ catalysis, ꢀ andꢀ energyꢀ storage. ꢀ Althoughꢀ aꢀ usedꢀ toꢀ produceꢀ theꢀ desiredꢀ AIE-basedꢀ luminescence.ꢀ Developingꢀ
numberꢀ ofꢀ POPsꢀ suchꢀ asꢀ conjugatedꢀ microporousꢀ polymersꢀ POPsꢀthatꢀcanꢀundergoꢀESIPTꢀcouldꢀprovideꢀanꢀalternativeꢀstrategyꢀ
[
15]ꢀ
[16]
(
CMPs),
polymersꢀ ofꢀ intrinsicꢀ microporosityꢀ (PIMs), ꢀ porousꢀ forꢀconstructingꢀluminescentꢀmaterialsꢀwithoutꢀrelyingꢀonꢀtheꢀπ-πꢀ
[17]
aromaticꢀ frameworksꢀ (PAFs), ꢀ covalentꢀ triazineꢀ frameworksꢀ interactionsꢀ ofꢀ carefullyꢀ selectedꢀ π-conjugatedꢀ monomers.ꢀ Suchꢀ
[
18]
[19]
(
CTFs), ꢀcovalentꢀorganicꢀpolymersꢀ(COPs) andꢀporousꢀpolymerꢀ investigationsꢀ couldꢀ alsoꢀ beꢀ usefulꢀ forꢀ designingꢀ otherꢀ novelꢀ 2Dꢀ
polymericꢀsystemsꢀforꢀoptoelectronicꢀapplications.ꢀꢀ
ꢀ
Herein,ꢀweꢀreportꢀtheꢀsynthesisꢀofꢀthreeꢀimine-linkedꢀ2DꢀTSA-
POPsꢀ containingꢀ C -symmetricꢀ 1,3,5-triarylbenzeneꢀ (TAB),ꢀ -
3
tristyrylbenzeneꢀ (TSB),ꢀ andꢀ -tris(arylethynyl)benzeneꢀ (TAE)ꢀ
monomerꢀunits.ꢀꢀWeꢀꢀdemonstrateꢀꢀthatꢀꢀtheꢀꢀpreformedꢀꢀC=NŸŸŸH-Oꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ1ꢀꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

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DOI: 10.1039/C7TC00123A
JournalꢀNameꢀ
ꢀ
COMMUNICATIONꢀ
BDP
CHO
HO
Dimethylacetamide / 1,2-Dichlorobenzene
Dimethylacetamide / 1,2 Dichlorobenzene
20 °C / 3 days
°
NH
2
1
95
C / 3 days
NH
2
OH
CHO
NH
2
Dimethylacetamide / Toluene
H
2
N
20 °C / 3 days
H2
N
NH2
1
TSB
NH
2
TAE
H
2
N
NH
2
TAB
OH
N
N
OH
N
OH
N
N
HO
OH
N
N
HO
OH
N
HO
OH
N
N HO
N HO
N HO
N
N
N
N
N
HO
N
HO
HO
HO
HO
HO
TSA-POP 1
TSA-POP 2
TSA-POP 3
OH
OH
OH
OH
OH
N
OH
N
N
N
N
N
OH
N
N
OH
N
OH
OH
N
HO
N
N
N
N HO
HO
HO
OH
OH
N
N
N HO
N HO
Schemeꢀ2ꢀꢀSynthesisꢀofꢀtheꢀTSA-POPsꢀ1-3.ꢀ
bondsꢀofꢀtheꢀTSA-POPsꢀcanꢀundergoꢀꢀESIPTꢀtoꢀproduceꢀfluorescentꢀ POPsꢀ (Fig.ꢀ S11-S13,ꢀ ESI).ꢀ Theꢀ presenceꢀ ofꢀ theꢀ alkeneꢀ andꢀ alkynylꢀ
materialsꢀ withꢀ respectableꢀ surfaceꢀ areas.ꢀ Theꢀ TSA-POPsꢀꢀꢀꢀꢀꢀ uꢀ ꢀ nꢀ ꢀ ꢀi ꢀtꢀ sꢀ ꢀ ꢀꢀ forꢀTSA-POPꢀ1ꢀandꢀ3ꢀwereꢀconfirmedꢀatꢀresonancesꢀofꢀ~127.9ꢀ
2+
alsoꢀexperienceꢀquenchingꢀofꢀfluorescenceꢀinꢀtheꢀpresenceꢀofꢀCu ꢀ andꢀ90.8ꢀppm,ꢀrespectively.ꢀPowderꢀx-rayꢀdiffractionꢀ(PXRD)ꢀprofilesꢀ
2+
andꢀ Pd ꢀ metalꢀ ionsꢀ makingꢀ themꢀ potentiallyꢀ usefulꢀ forꢀ sensoryꢀ ofꢀtheꢀTSA-POPsꢀrevealedꢀnoꢀpeaksꢀindicatingꢀthatꢀtheꢀmaterialsꢀareꢀ
ꢀ
[22]
applications. ꢀꢀꢀꢀꢀ
ꢀꢀTheꢀ imine-linkedꢀ POPsꢀ wereꢀ synthesizedꢀ byꢀ reactingꢀ theꢀ aminoꢀ ꢀꢀꢀTheꢀ porosityꢀ ofꢀ theꢀ TSA-POPsꢀ wasꢀ evaluatedꢀ usingꢀ nitrogenꢀ gasꢀ
functionalizedꢀ TSB,ꢀ TAB,ꢀ andꢀ TAEꢀ monomersꢀ withꢀ 3,3'-dihydroxy- adsorptionꢀ isothermsꢀ atꢀ 77ꢀ Kꢀ (Fig.ꢀ 1).ꢀ Allꢀ threeꢀ ofꢀ theꢀ TSA-POPsꢀ
1,1'-biphenyl]-4,4'-dicarbaldehydeꢀ (BDP)ꢀ inꢀ aꢀ mixtureꢀ ofꢀ solventsꢀ exhibitedꢀreversibleꢀtypeꢀIVꢀisotherms,ꢀwhichꢀisꢀindicativeꢀofꢀtheirꢀ
containingꢀ 6Mꢀ aceticꢀ acidꢀ atꢀ 95°Cꢀ orꢀ 120ꢀ °Cꢀ forꢀ threeꢀ daysꢀ toꢀ mesoporosity.ꢀ Applyingꢀ theꢀ Brunauer-Emmett-Tellerꢀ (BET)ꢀ modelꢀ
produceꢀTSA-POPsꢀ1-3,ꢀrespectivelyꢀ(Schemeꢀ2).ꢀTheꢀTSA-POPsꢀwereꢀ overꢀ theꢀ low-pressureꢀ regionꢀ (0.04ꢀ <ꢀ P/P ꢀ <ꢀ 0.24-0.29)ꢀ providedꢀ
amorphousꢀandꢀexhibitꢀnoꢀlong-rangeꢀorderꢀ(FigꢀS14-S16,ꢀESI).ꢀꢀ
ꢀ
[
0
2
-1
obtainedꢀ byꢀ filtrationꢀ andꢀ washedꢀ withꢀ tetrahydrofuranꢀ (THF)ꢀ toꢀ surfaceꢀareasꢀofꢀ601,ꢀ427,ꢀandꢀ135ꢀm ꢀg ꢀforꢀTSA-POPꢀ1,ꢀ2,ꢀandꢀ3,ꢀ
obtainꢀyellowꢀpowdersꢀthatꢀwereꢀinsolubleꢀinꢀorganicꢀsolvents.ꢀTheꢀ respectivelyꢀ (Fig.ꢀ S23-S25,ꢀ ESI).ꢀ Theꢀ nonlocalꢀ densityꢀ functionalꢀ
optimalꢀ reactionꢀ conditionsꢀ wereꢀ obtainedꢀ byꢀ screeningꢀ differentꢀ theoryꢀꢀ(NLDFT)ꢀporeꢀsizeꢀdistributionsꢀrevealedꢀmajorꢀpeaksꢀatꢀ2.1,ꢀꢀ
solventꢀmixtures,ꢀreactionꢀtimes,ꢀandꢀtemperaturesꢀ(TablesꢀS1-S3,ꢀ _______________________________________________________ꢀ
ESI).ꢀ Thermogravimetricꢀ analysisꢀ (TGA)ꢀ impliedꢀ thatꢀ theꢀ TSA-POPsꢀ (a)ꢀ2
(b)ꢀ0.25ꢀ
50ꢀ
00ꢀ
50ꢀ
00ꢀ
areꢀstableꢀupꢀtoꢀ400ꢀ°Cꢀ(FigꢀS2-S4,ꢀESI),ꢀwhileꢀtheꢀscanningꢀelectronꢀ
0.2ꢀ
2
microscopyꢀ (SEM)ꢀ imagesꢀ revealedꢀ aꢀ cauliflower-likeꢀ morphologyꢀ
0.15ꢀ
1
forꢀtheꢀmaterialsꢀ(FigꢀS5-S7,ꢀESI).ꢀꢀ
0.1ꢀ
1
ꢀ
ꢀꢀTheꢀ TSA-POPsꢀ wereꢀ characterizedꢀ usingꢀ Fourierꢀ Transformꢀ
0.05ꢀ
0ꢀ
13
5
0ꢀ
infraredꢀ(FT-IR)ꢀandꢀ Cꢀcross-polarizationꢀmagicꢀangleꢀspinningꢀ(CP-
MAS)ꢀ NMRꢀ spectroscopies.ꢀ Theꢀ FT-IRꢀ spectraꢀ revealedꢀ theꢀ
characteristicꢀ C=Nꢀ stretchingꢀ vibrationsꢀ forꢀ theꢀ imine-linkageꢀ atꢀꢀꢀꢀꢀꢀꢀ
0ꢀ
0ꢀ
0.2ꢀ
0.4ꢀ
0.ꢁꢀ
0.8ꢀ
1ꢀ
1.7ꢀ
2.7ꢀ
3.7ꢀ
4.7ꢀ
5.7ꢀ
Rela6veꢀPressureꢀ(P/Po)ꢀ
PoreꢀWidthꢀ(nm)ꢀ
ꢀ
-1ꢀ
13
~
1612ꢀcm (Fig.ꢀS8-S10,ꢀESI).ꢀTheꢀ CꢀCP-MASꢀspectraꢀdisplayedꢀtheꢀ Fig.ꢀ 1ꢀ Nitrogenꢀ adsorption-desorptionꢀ isothermsꢀ (a)ꢀ andꢀ NLDFTꢀ poreꢀ sizeꢀ
distinctꢀresonanceꢀforꢀtheꢀC=Nꢀbondꢀatꢀ~161ꢀppmꢀforꢀallꢀofꢀtheꢀTSA- distributionsꢀ (b)ꢀ forꢀ TSA-POP-1ꢀ (green),ꢀ TSA-POP-2ꢀ (red),ꢀ andꢀ TSA-POP-3ꢀ
blue)ꢀmeasuredꢀatꢀ77ꢀK.ꢀ
(
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ2ꢀꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

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JournalꢀNameꢀ
a)ꢀ
ꢀCOMMUNICATIONꢀ
(
(b)ꢀ
(a)ꢀ
(b)ꢀ
View Article Online
DOI: 10.1039/C7TC00123A
1ꢀ
700ꢀ
800ꢀ
600ꢀ
400ꢀ
200ꢀ
0ꢀ
600ꢀ
500ꢀ
400ꢀ
0
.8ꢀ
.6ꢀ
.4ꢀ
.2ꢀ
0
0
0
TSA-POPꢀ1ꢀ
TSA-POPꢀ2ꢀ
300ꢀ
200ꢀ
100ꢀ
0ꢀ
Fꢀ Li+ꢀ
+ꢀ
Ag
g2+ꢀ
+ꢀ
+ꢀ
d2+ꢀ u2+ꢀ
C
Fꢀ Li+ꢀ
+ꢀ
Ag
g2+ꢀ
+ꢀ
+ꢀ
2
d2+ꢀ u2+ꢀ
P C
0ꢀ
TH
3
Fe
2
TH
3
Fe
H
Zn
P
H
Zn
5
20ꢀ 545ꢀ 570ꢀ 595ꢀ 620ꢀ 645ꢀ 670ꢀ
(
c)ꢀ
(d)ꢀ
Wavelengthꢀ(nm)ꢀ
TSA-POPꢀ3ꢀ
ꢀ
400ꢀ
300ꢀ
(1)ꢀ
Fig.ꢀ 2ꢀ ꢀ Solid-Stateꢀ emissionꢀ spectraꢀ (a)ꢀ ofꢀ TSA-POPꢀ 1ꢀ (red),ꢀ TSA-POPꢀ 2ꢀ
green),ꢀandꢀTSA-POPꢀ3ꢀ(blue).ꢀ(b)ꢀPhotographsꢀofꢀtheꢀluminescentꢀTSA-POPsꢀ
takenꢀusingꢀaꢀhand-heldꢀUV-lampꢀatꢀ365ꢀnm.ꢀ
(
ꢀ(2)ꢀ
(3)ꢀ
2
00ꢀ
00ꢀ
0ꢀ
1
_
ꢀ
_____________________________________________________________ꢀ
ꢀ
Fꢀ Li+ꢀ
+ꢀ
Ag
+ꢀ
+ꢀ
+ꢀ
+ꢀ
+ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
H
2
3
Fe
2
2
2
u
C
ꢀTHF Li ꢀAgꢀHg ꢀFe ꢀZn ꢀPd ꢀCu
2
.1,ꢀandꢀ2.5ꢀnmꢀforꢀTSA-POPꢀ1,ꢀ2,ꢀandꢀ3,ꢀrespectively,ꢀinꢀadditionꢀtoꢀ
otherꢀporesꢀthatꢀextendꢀintoꢀtheꢀmesoporousꢀrange.ꢀꢀTheꢀtotalꢀporeꢀ
volumes,ꢀwhichꢀwereꢀcalculatedꢀatꢀsingleꢀpointꢀvaluesꢀ(P/P ꢀ=ꢀ0.94,ꢀ
T
g
Zn
d
H
P
ꢀ
Fig.ꢀ4ꢀꢀꢀEmissionꢀintensitiesꢀofꢀTSA-POPꢀ1ꢀ(a),ꢀTSA-POPꢀ2ꢀ(b),ꢀandꢀTSA-POPꢀ3ꢀ
(c)ꢀ suspendedꢀ inꢀ THFꢀ beforeꢀ andꢀ afterꢀ theꢀ additionꢀ ofꢀ metalꢀ ions.ꢀ (d)ꢀ
PhotographsꢀofꢀTSA-POPꢀ1ꢀ(1),ꢀTSA-POPꢀ2ꢀ(2),ꢀandꢀTSA-POPꢀ3ꢀ(3)ꢀsuspendedꢀ
inꢀTHFꢀbeforeꢀandꢀafterꢀtheꢀadditonꢀofꢀmetalꢀions.ꢀTheꢀpicturesꢀwereꢀtakenꢀ
0
3
-1
0
.90,ꢀ0.89),ꢀprovidedꢀvaluesꢀofꢀ0.40,ꢀ0.20,ꢀandꢀ0.12ꢀcm ꢀg ꢀforꢀTSA-
POPꢀ1,ꢀ2,ꢀandꢀ3,ꢀrespectively.ꢀ
ꢀ
ꢀꢀTheꢀsolid-stateꢀemissionꢀspectraꢀandꢀluminescentꢀphotographsꢀofꢀ takenꢀusingꢀaꢀhand-heldꢀUV-lampꢀatꢀ365ꢀnm.ꢀ
TSA-POPsꢀ1,ꢀ2,ꢀandꢀ3ꢀareꢀshownꢀinꢀFig.ꢀ2.ꢀTSA-POPꢀ2ꢀandꢀ3ꢀexhibitꢀaꢀ
maxꢀ ofꢀ 565ꢀ nmꢀ andꢀ 567ꢀ nm,ꢀ respectively.ꢀ Inꢀ comparison,ꢀ theꢀ
emissionꢀmaximaꢀofꢀTSA-POPꢀ1ꢀdisplaysꢀaꢀbathochromicꢀshiftꢀofꢀ~ꢀ8-
0ꢀ nmꢀ withꢀ aꢀ λmaxꢀ ofꢀ 575ꢀ nm.ꢀ Theꢀ bathochromicꢀ shiftꢀ couldꢀ beꢀ
_
ꢀ
_____________________________________________________________ꢀ
λ
emissionꢀ bandsꢀ ofꢀ theꢀ TSA-POPsꢀ beganꢀ toꢀ decreaseꢀ inꢀ intensity,ꢀ
whichꢀeventuallyꢀleadsꢀtoꢀtheꢀquenchingꢀofꢀfluorescenceꢀ(Figꢀ3a-3c).ꢀ
Weꢀ believeꢀ theꢀ quenchingꢀ ofꢀ fluorescenceꢀ isꢀ attributedꢀ toꢀ theꢀ
suppressionꢀ ofꢀ theꢀ enol-ketoꢀ tautomerizationꢀ inꢀ theꢀ excited-stateꢀ
dueꢀꢀtoꢀꢀtheꢀꢀprotonationꢀꢀofꢀꢀtheꢀꢀimineꢀꢀnitrogenꢀꢀatomsꢀ(Fig.ꢀ3d).ꢀInꢀ
addition,ꢀitꢀshouldꢀbeꢀnotedꢀthatꢀtheꢀsolid-stateꢀfluorescenceꢀofꢀtheꢀ
TSA-POPsꢀ isꢀ highlyꢀ dependentꢀ onꢀ theꢀ structureꢀ ofꢀ theꢀ aldehydeꢀ
precursor.ꢀ Forꢀ example,ꢀ itꢀ hasꢀ beenꢀ shownꢀ thatꢀ aꢀ 2,5-
1
attributedꢀtoꢀtheꢀrestrictedꢀrotationꢀofꢀtheꢀalkeneꢀunitsꢀofꢀtheꢀTSBꢀ
linker,ꢀ whichꢀ leadsꢀ toꢀ enhancedꢀ π-conjugationꢀ byꢀ reducingꢀ theꢀ
energyꢀgapꢀofꢀtheꢀπ−π*ꢀtransitionꢀforꢀTSA-POPꢀ1.ꢀꢀThisꢀphenomenonꢀ
isꢀ consistentꢀ withꢀ whatꢀ hasꢀ beenꢀ observedꢀ forꢀ theꢀ previouslyꢀ
[9]
reportedꢀalkene-basedꢀTSAꢀanalog. ꢀInterestingly,ꢀtheꢀTABꢀandꢀTAEꢀ
linkersꢀ doꢀ notꢀ appearꢀ toꢀ haveꢀ aꢀ significantꢀ effectꢀ onꢀ theꢀ bulkꢀ
fluorescentꢀ propertiesꢀ ofꢀ theꢀ materials.ꢀUV-Visꢀ diffuseꢀ reflectanceꢀ
spectraꢀ showꢀ thatꢀ theꢀ TSA-POPsꢀ exhibitꢀ broadꢀ absorptionꢀ bandsꢀ
thatꢀextendꢀfromꢀ380ꢀnmꢀtoꢀ550ꢀnmꢀ(Fig.ꢀS17,ꢀESI).ꢀꢀ
ꢀ
dihydroxyterephthalaldehydeꢀ (Dha)ꢀlinkerꢀcanꢀbeꢀusedꢀtoꢀconstructꢀ
[23]
crystallineꢀimine-linkedꢀcovalentꢀorganicꢀframeworksꢀ(COFs) ,ꢀbutꢀ
toꢀtheꢀbestꢀofꢀourꢀknowledgeꢀtheꢀmaterialsꢀdoꢀnotꢀundergoꢀESIPTꢀinꢀ
ꢀ
ꢀꢀInꢀ anꢀ effortꢀ toꢀ verifyꢀ thatꢀ theꢀ materialsꢀ areꢀ indeedꢀ undergoingꢀ
theꢀ solid-state.ꢀ Toꢀ verifyꢀ this,ꢀ weꢀ constructedꢀ theꢀ COF-DhaTabꢀ
ESIPT,ꢀ weꢀ titratedꢀ suspensionsꢀ ofꢀ theꢀ TSA-POPsꢀ inꢀ THFꢀ withꢀ
trifluoroaceticꢀacidꢀꢀ(TFA).ꢀꢀUponꢀtheꢀꢀadditionꢀꢀofꢀꢀ0-75ꢀꢀμLꢀꢀTFA,ꢀꢀtheꢀꢀ
[23c]
previouslyꢀ reportedꢀ byꢀ Banerjee
ꢀ andꢀ comparedꢀ it'sꢀ
photophysicalꢀ propertiesꢀ toꢀ TSA-POPꢀ 2,ꢀ whichꢀ containsꢀ theꢀ
extendedꢀBPDꢀlinker.ꢀSurprisingly,ꢀCOF-DhaTabꢀwasꢀnotꢀfluorescentꢀ
inꢀ theꢀ solid-state,ꢀ whileꢀ TSA-POPꢀ 2ꢀ exhibitedꢀ aꢀ brightꢀ yellowꢀ
fluorescentꢀ colorꢀ (Fig.ꢀ S18,ꢀ ESI).ꢀ Weꢀ believeꢀ theꢀ absenceꢀ ofꢀ
fluorescenceꢀforꢀCOF-DhaTabꢀcouldꢀbeꢀattributedꢀtoꢀ1)ꢀtheꢀabilityꢀofꢀ
theꢀ stackedꢀ layersꢀ toꢀ undergoꢀ anꢀ ACQꢀ mechanism,ꢀ orꢀ 2)ꢀ theꢀ
weakenedꢀphotoacidityꢀofꢀtheꢀDhaꢀhydroxylꢀgroupsꢀdueꢀtoꢀhavingꢀ
bothꢀsubstituentsꢀattachedꢀtoꢀtheꢀsameꢀphenylꢀring.ꢀTheꢀlatterꢀcouldꢀ
inhibitꢀ theꢀ abilityꢀ ofꢀ theꢀ preformedꢀ C=NŸŸŸH-Oꢀ bondsꢀ toꢀ undergoꢀ
ESIPTꢀinꢀtheꢀsolid-state.ꢀ
(
a)ꢀ
(b)ꢀ
0
ꢀμLꢀ
TFAꢀ
5ꢀμLꢀ
0ꢀμLꢀ
TFAꢀ
7
75ꢀμLꢀ
ꢀ
ꢀꢀꢀInꢀanꢀeffortꢀtoꢀexploreꢀtheꢀabilityꢀofꢀtheꢀTSA-POPsꢀtoꢀfunctionꢀasꢀ
Wavelengthꢀ(nm)ꢀ
Wavelengthꢀ(nm)ꢀ
fluorescentꢀ probesꢀ forꢀ metalꢀ ionsꢀ onꢀ accountꢀ ofꢀ theirꢀ preformedꢀ
c)ꢀ
(d)ꢀ
C=NŸŸŸH-Oꢀ bonds,ꢀ weꢀ evaluatedꢀ theꢀ chemosensingꢀ abilityꢀ ofꢀ theꢀ
(
0
ꢀμLꢀ
+
+
2+
3+
2+
2+
2+
hνꢀ
materialsꢀinꢀtheꢀpresenceꢀofꢀLi ,ꢀAg ,ꢀHg ,ꢀFe ,ꢀZn ,ꢀPd ,ꢀandꢀCu ꢀ
inꢀ THFꢀ (Fig.ꢀ 4).ꢀ TSA-POPꢀ 1,ꢀ 2ꢀ andꢀ 3ꢀ allꢀ undergoꢀ quenchingꢀ ofꢀ
N
H
O
NH
OH transfer
NH
O
TFAꢀ
No proton
2+
2+
H+
fluorescenceꢀuponꢀtheꢀexcessꢀadditionꢀofꢀ180ꢀμMꢀPd ꢀandꢀCu ꢀinꢀ
tetrahydrofuranꢀ(THF)ꢀ(Fig.ꢀS19-S21,ꢀESI).ꢀInterestingly,ꢀtheꢀadditionꢀ
7
5ꢀμLꢀ
O
H
HO
HN
HO
HN
2+
N
ofꢀZn ꢀresultsꢀinꢀaꢀdecreaseꢀinꢀemissionꢀintensityꢀforꢀtheꢀTSA-POPs,ꢀ
whichꢀisꢀdifferentꢀinꢀcontrastꢀtoꢀtheꢀenhancementꢀinꢀfluorescenceꢀ
Wavelengthꢀ(nm)ꢀ
[9]
ꢀ
thatꢀ wasꢀ experiencedꢀ forꢀ theꢀ TSAꢀ analogs. ꢀ Theꢀ differenceꢀ inꢀ
Fig.ꢀ3ꢀꢀꢀEmissionꢀtitrationꢀspectraꢀofꢀTSA-POPꢀ1ꢀ(a),ꢀTSA-POPꢀ2ꢀ(b),ꢀandꢀTSA- fluorescentꢀ propertiesꢀ couldꢀ beꢀ attributedꢀ toꢀ theꢀ inabilityꢀ ofꢀ theꢀ
2
+
POPꢀ3ꢀ(c)ꢀwithꢀTFAꢀsuspendedꢀinꢀTHF.ꢀ(d)ꢀSchematicꢀrepresentationꢀofꢀTFAꢀ
inhibitingꢀtheꢀESIPTꢀtautomerizationꢀprocess.ꢀꢀ
rigidꢀ TSA-POPsꢀ toꢀ formꢀ 1:2ꢀ complexesꢀ withꢀ Zn ,ꢀ whichꢀ couldꢀ
impedeꢀ anꢀ efficientꢀ metal-to-ligandꢀ chargeꢀ transferꢀ (MLCT)ꢀ orꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ3ꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Jo uP rl ne aa sl eo ꢀ fd Mo ꢀ an to et rꢀ ai ad l jsu sC t hꢀ me am r ig si nt rsyꢀ C
Page 4 of 6
COMMUNICATIONꢀ
ligand-to-metalꢀchargeꢀtransferꢀ(LMCT)ꢀprocess.ꢀSuspensionsꢀofꢀtheꢀ
JournalꢀNameꢀ
Macromoleculesꢀ2000,ꢀ33,ꢀ7223-7225;ꢀ(c)ꢀSV.ꢀiePwarAkrt,icꢀSle.ꢀOKnilmine,ꢀ
J.ꢀ Seo,ꢀ S.ꢀ Y.ꢀ Park,ꢀ Macromolecule sD ꢀ O2 I0: 01 05 .,1ꢀ 03 38 9, /ꢀ C4 75 T5 C7 0- 40 51 25 39A ;ꢀ
d)ꢀ K.ꢀ Kanosue,ꢀ R.ꢀ Augulis,ꢀ D.ꢀ Peckus,ꢀ R.ꢀ Karpicz,ꢀ T.ꢀ
Tamulevičius,ꢀ S.ꢀ Tamulevičius,ꢀ V.ꢀ Gulbinas,ꢀ S.ꢀ Ando,ꢀ
Macromoleculesꢀ2016,ꢀ49,ꢀ1848-1857.ꢀꢀꢀꢀꢀꢀ
J.ꢀW.ꢀColson,ꢀW.ꢀR.ꢀDichtel,ꢀNat.ꢀChem.ꢀ2013,ꢀ5,ꢀ453–465.ꢀ
P.ꢀ Jagadesan,ꢀ T.ꢀ Whittemore,ꢀ T.ꢀ Beirl,ꢀ C.ꢀ Turro,ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
P.ꢀ L.ꢀ McGrier,ꢀ Chem.ꢀ Eur.ꢀ Jꢀ 2016,ꢀ DOI:ꢀ
+
+
2+
3+ꢀ
TSA-POPsꢀwereꢀunresponsiveꢀtoꢀLi ,ꢀAg ,ꢀHg ,ꢀandꢀFe inꢀTHFꢀ(Fig.ꢀ
S22,ꢀESI).ꢀ
(
ꢀ
3
ꢀꢀInꢀ conclusion,ꢀ weꢀ haveꢀ demonstratedꢀ thatꢀ aꢀ BDPꢀ linkerꢀ andꢀ C -
symmetricꢀ amino-functionalizedꢀ monomersꢀ canꢀ beꢀ usedꢀ toꢀ
constructꢀimine-linkedꢀTSA-POPsꢀthatꢀcanꢀundergoꢀESIPTꢀtoꢀproduceꢀ
[
[
8]ꢀ
9]ꢀ
2+
luminescentꢀ materials.ꢀ Theꢀ TSA-POPsꢀ areꢀ alsoꢀ responsiveꢀ toꢀ Cu ꢀ
2+
andꢀ Pd ꢀ makingꢀ themꢀ potentiallyꢀ usefulꢀ asꢀ fluorescent-basedꢀ
1
0.1002/chem.201604315.ꢀ
[24]ꢀ
chemosensors. Toꢀ theꢀ bestꢀ ofꢀ ourꢀ knowledge,ꢀ thisꢀ isꢀ theꢀ firstꢀ
exampleꢀofꢀꢀ2DꢀPOPsꢀexhibitingꢀESIPTꢀinꢀtheꢀsolid-state.ꢀWeꢀbelieveꢀ
[
10]ꢀ
D.ꢀWu,ꢀF.ꢀXu,ꢀB.ꢀSun,ꢀR.ꢀFu,ꢀH.ꢀHe,ꢀK.ꢀMatyjaszewski,ꢀChem.ꢀ
Rev.ꢀ2012,ꢀ112,ꢀ3959-4015.ꢀ
suchꢀ investigationsꢀ areꢀ necessaryꢀ forꢀ notꢀ onlyꢀ advancingꢀ theꢀ [11]ꢀ
structuralꢀ diversityꢀ ofꢀ thisꢀ uniqueꢀ classꢀ ofꢀ materials,ꢀ butꢀ alsoꢀ
designingꢀnovelꢀfunctionalꢀ2Dꢀpolymersꢀforꢀpracticalꢀapplications.ꢀꢀ
(a)ꢀ R.ꢀ Dawson,ꢀ E.ꢀ Stockel,ꢀ J.ꢀ R.ꢀ Holst,ꢀ D.ꢀ J.ꢀ Adams,ꢀ A.ꢀ I.ꢀ
Cooper,ꢀEnergyꢀEnviron.ꢀSci.ꢀ2011,ꢀ4,ꢀ4239-4245;ꢀ(b)ꢀY.ꢀXie,ꢀ
T.-T.ꢀWang,ꢀX.-H.ꢀLiu,ꢀK.ꢀZou,ꢀW.-Q.ꢀDeng,ꢀNatꢀCommun.ꢀ
2
013,ꢀ 4,ꢀ 1960–1965.ꢀ (c)ꢀ H.ꢀ A.ꢀ Patel,ꢀ D.ꢀ Ko,ꢀ C.ꢀ T.ꢀ Yavuz,ꢀ
Acknowledgements
ꢀ
Chem.ꢀ Mater.ꢀ 2014,ꢀ 26,ꢀ 6729−6733;ꢀ (d)ꢀ S.ꢀ
Bandyopadhyay,ꢀA.ꢀG.ꢀAnil,ꢀA.ꢀJames,ꢀA.ꢀPatra,ꢀACSꢀAppl.ꢀ
Mater.ꢀInterfacesꢀ2016,ꢀ8,ꢀ27669−27678.ꢀꢀ
(a)ꢀC.ꢀD.ꢀWood,ꢀB.ꢀTan,ꢀA.ꢀTrewin,ꢀH.ꢀNiu,ꢀD.ꢀBradshaw,ꢀM.ꢀ
J.ꢀ Rosseinsky,ꢀ Y.ꢀ Z.ꢀ Khimyak,ꢀ N.ꢀ L.ꢀ Campbell,ꢀ R.ꢀ Kirk,ꢀ E.ꢀ
Stockel,ꢀA.ꢀI.ꢀCooper,ꢀChem.ꢀMater.ꢀ2007,ꢀ19,ꢀ2034–2048;ꢀ
P.L.Mꢀ acknowledgesꢀ theꢀ Nationalꢀ Scienceꢀ Foundationꢀ (NSF)ꢀ andꢀ
Georgiaꢀ Techꢀ Facilitatingꢀ Academicꢀ Careersꢀ inꢀ Engineeringꢀ andꢀ
Scienceꢀ(GT-FACES)ꢀforꢀaꢀCareerꢀInitiationꢀGrant,ꢀandꢀfundingꢀfromꢀ
Theꢀ Ohioꢀ Stateꢀ University.ꢀ Weꢀ thankꢀ Katjaꢀ Meyerꢀ andꢀ Dr.ꢀ Umitꢀ
OzkanꢀforꢀassistanceꢀwithꢀtheꢀTGAꢀmeasurements.ꢀꢀ
[
12]ꢀ
(
b)ꢀC.ꢀD.ꢀWood,ꢀB.ꢀTan,ꢀA.ꢀTrewin,ꢀF.ꢀSu,ꢀM.ꢀJ.ꢀRosseinsky,ꢀ
D.ꢀ Bradshaw,ꢀ Y.ꢀ Sun,ꢀ L.ꢀ Zhou,ꢀ A.ꢀ I.ꢀ Cooper,ꢀ Adv.ꢀ Mater.ꢀ
008,ꢀ20,ꢀ1916–1921;ꢀ(c)ꢀS.ꢀYuan,ꢀB.ꢀDorney,ꢀD.ꢀWhite,ꢀS.ꢀ
Kirklin,ꢀP.ꢀZapol,ꢀL.ꢀYu,ꢀD.-J.ꢀLiu,ꢀChem.ꢀCommun.ꢀ2010,ꢀ46,ꢀ
547–4549.ꢀ
P.ꢀKaur,ꢀJ.ꢀT.ꢀHupp,ꢀS.ꢀT.ꢀNguyen,ꢀACSꢀCatal.ꢀ2011,ꢀ1,ꢀ819–
35.ꢀ
Notesꢀandꢀreferencesꢀ
2
[
1]ꢀ
(a)ꢀ C.-C.ꢀ Hsieh,ꢀ C.-M.ꢀ Jiang,ꢀ P.-T.ꢀ Chou,ꢀ Acc.ꢀ Chem.ꢀ Res.ꢀ
2
2
010,ꢀ43,ꢀ1364-1374;ꢀ(b)ꢀJ.ꢀE.ꢀKwon,ꢀS.ꢀY.ꢀPark,ꢀAdv.ꢀMater.ꢀ
011,ꢀ23,ꢀ3615–3642;ꢀ(c)ꢀV.ꢀI.ꢀTomin,ꢀA.ꢀP.ꢀDemchenko,ꢀP.-
4
[
[
13]ꢀ
14]ꢀ
T.ꢀChou,ꢀJ.ꢀPhotochem.ꢀPhotobiol.,ꢀCꢀꢀ2015,ꢀ22,ꢀ1-18.ꢀ(d)ꢀV.ꢀ
S.ꢀPadalkar,ꢀS.ꢀSeki,ꢀChem.ꢀSoc.ꢀRev.ꢀ2016,ꢀ45,ꢀ169-202.ꢀꢀ
(a)ꢀA.ꢀU.ꢀKhan,ꢀM.ꢀKasha,ꢀProc.ꢀNatl.ꢀAcad.ꢀSci.ꢀUSAꢀ1983,ꢀ
8
(a)ꢀJ.-X.ꢀJiang,ꢀA.ꢀTrewin,ꢀD.ꢀJ.ꢀAdams,ꢀA.ꢀI.ꢀCooper,ꢀChem.ꢀ
Sci.ꢀ2011,ꢀ2,ꢀ1777-1781;ꢀ(b)ꢀA.ꢀThomas,ꢀP.ꢀKuhn,ꢀJ.ꢀWeber,ꢀ
M.-M.ꢀ Titirici,ꢀ M.ꢀ Antonietti,ꢀ Macromol.ꢀ Rapidꢀ Commun.ꢀ
[
[
2]ꢀ
3]ꢀ
8
0,ꢀ1767ꢀ–1770.ꢀ(b)ꢀK.-i.ꢀSakai,ꢀM.ꢀIchikawa,ꢀY.ꢀTaniguchi,ꢀ
Chem.ꢀPhys.ꢀLett.ꢀ2006,ꢀ420,ꢀ405-409.ꢀꢀ
2
009,ꢀ30,ꢀ221–236.ꢀ
(a)ꢀ M.ꢀ J.ꢀ Paterson,ꢀ M.ꢀ A.ꢀ Robb,ꢀ L.ꢀ Blancafort,ꢀ A.ꢀ D.ꢀ
DeBellis,ꢀ J.ꢀ Phys.ꢀ Chem.ꢀ Aꢀ 2005,ꢀ 109,ꢀ 7527–7537;ꢀ (b)ꢀ Y.ꢀ
Gong,ꢀZ.ꢀWang,ꢀS.ꢀZhang,ꢀZ.ꢀLuo,ꢀF.ꢀGao,ꢀH.ꢀLi,ꢀInd.ꢀEng.ꢀ
Chem.ꢀRes.ꢀ2016,ꢀ55,ꢀ5223–5230.ꢀ
[
15]ꢀ
(a)ꢀJ.-X.ꢀJiang,ꢀF.ꢀSu,ꢀA.ꢀTrewin,ꢀC.ꢀD.ꢀWood,ꢀN.ꢀL.ꢀCampbell,ꢀ
H.ꢀ Niu,ꢀ C.ꢀ Dickinson,ꢀ A.ꢀ Y.ꢀ Ganin,ꢀ M.ꢀ J.ꢀ Rosseinsky,ꢀ Y.ꢀ Z.ꢀ
Khimyak,ꢀ A.ꢀ I.ꢀ Cooper,ꢀ Angew.ꢀ Chem.ꢀ Int.ꢀ Ed.ꢀ 2007,ꢀ 46,ꢀ
8
574ꢀ–8578;ꢀ(b)ꢀL.ꢀChen,ꢀY.ꢀHonsho,ꢀS.ꢀSeki,ꢀD.ꢀJiang,ꢀJ.ꢀAm.ꢀ
[
4]ꢀ
(a)ꢀQ.ꢀChu,ꢀD.ꢀA.ꢀMedvetz,ꢀY.ꢀPang,ꢀChem.ꢀMater.ꢀ2007,ꢀ19,ꢀ
Chem.ꢀSoc.ꢀ2010,ꢀ132,ꢀ6742−6748;ꢀ(c)ꢀG.ꢀCheng,ꢀT.ꢀHasell,ꢀ
A.ꢀTrewin,ꢀD.ꢀJ.ꢀAdams,ꢀA.ꢀI.ꢀCooper,ꢀAngew.ꢀChem.ꢀInt.ꢀEd.ꢀ
6
421–6429;ꢀ(b)ꢀB.ꢀLiu,ꢀH.ꢀWang,ꢀT.ꢀWang,ꢀY.ꢀBao,ꢀF.ꢀDu,ꢀJ.ꢀ
Tian,ꢀQ.ꢀLi,ꢀR.ꢀBai,ꢀChem.ꢀCommun.ꢀ2012,ꢀ48,ꢀ2867-2869;ꢀ
c)ꢀ J.ꢀ Zhao,ꢀ S.ꢀ Ji,ꢀ Y.ꢀ Chen,ꢀ H.ꢀ Guo,ꢀ P.ꢀ Yang,ꢀ Phys.ꢀ Chem.ꢀ
2
012,ꢀ 51,ꢀ 12727-12731;ꢀ (d)ꢀ B.ꢀ Bonillo,ꢀ R.ꢀ S.ꢀ Sprick,ꢀ A.ꢀ I.ꢀ
(
Cooper,ꢀChem.ꢀMater.ꢀ2016,ꢀ28,ꢀ3469−3480.ꢀ
N.ꢀ B.ꢀ McKeown,ꢀ P.ꢀ M.ꢀ Budd,ꢀ Chem.ꢀ Soc.ꢀ Rev.ꢀ 2006,ꢀ 35,ꢀ
Chem.ꢀPhys.ꢀ2012,ꢀ14,ꢀ8803-8817.ꢀ
[
16]ꢀ
[
[
5]ꢀ
6]ꢀ
S.-J.ꢀLim,ꢀJ.ꢀSeo,ꢀS.ꢀY.ꢀPark,ꢀJ.ꢀAm.ꢀChem.ꢀSocꢀ2006,ꢀ128,ꢀ
6
75–683.ꢀ
1
4542-14547.ꢀ
(a)ꢀT.ꢀArthen-Engeland,ꢀT.ꢀBultmann,ꢀN.ꢀP.ꢀErnsting,ꢀM.ꢀA.ꢀ
Rodriguez,ꢀW.ꢀThielꢀChem.ꢀPhys.ꢀ1992,ꢀ163,ꢀ43-53;ꢀ(b)ꢀD.ꢀ
[
[
17]ꢀ
18]ꢀ
T.ꢀBen,ꢀS.ꢀQiu,ꢀCrystEngCommꢀ2013,ꢀ15,ꢀ17-26.ꢀ
C.ꢀE.ꢀChan-Thaw,ꢀA.ꢀVilla,ꢀP.ꢀKatekomol,ꢀD.ꢀSu,ꢀA.ꢀThomas,ꢀ
L.ꢀPrati,ꢀNanoꢀLett.ꢀ2010,ꢀ10,ꢀ537–541.ꢀ
ꢁ
W.ꢀ Brousmiche,ꢀ P.ꢀ Wan,ꢀ J.ꢀ Photochem.ꢀ Photobiol.ꢀ A:ꢀ
Chem.ꢀ 2000,ꢀ 130,ꢀ 113-118;ꢀ (c)ꢀ N.ꢀ Otsubo,ꢀ C.ꢀ Okabe,ꢀ H.ꢀ
Mori,ꢀ K.ꢀ Sakota,ꢀ K.ꢀ Amimoto,ꢀ T.ꢀ Kawato,ꢀ H.ꢀ Sekiya,ꢀ J.ꢀ
Photochem.ꢀPhoto-ꢀbiol.ꢀAꢀ 2002,ꢀ154,ꢀ33−39ꢀ;ꢀ(d)ꢀM.-W.ꢀ
Chung,ꢀT.-Y.ꢀLin,ꢀC.-C.ꢀHsieh,ꢀK.-C.ꢀTang,ꢀH.ꢀFu,ꢀP.-T.ꢀChou,ꢀ
S.-H.ꢀYang,ꢀY.ꢀChi,ꢀJ.ꢀPhys.ꢀChem.ꢀAꢀ2010,ꢀ114,ꢀ7886–7891;ꢀ
[
[
19]ꢀ
20]ꢀ
Z.ꢀXiang,ꢀD.ꢀCao,ꢀL.ꢀDai,ꢀPolym.ꢀChem.ꢀ2015,ꢀ6,ꢀ1896-1911.ꢀ
Y.ꢀZhu,ꢀH.ꢀLong,ꢀW.ꢀZhang,ꢀChem.ꢀMater.ꢀ2013,ꢀ25,ꢀ1630–
1
635.ꢀ
[
[
21]ꢀ
22]ꢀ
S.ꢀDalapati,ꢀC.ꢀGu,ꢀD.ꢀJiang,ꢀSmallꢀ2016,ꢀ12,ꢀ6513-6527.ꢀ
(a)ꢀW.-L.ꢀGong,ꢀM.ꢀP.ꢀAldred,ꢀG.-F.ꢀZhang,ꢀC.ꢀLi,ꢀM.-Q.ꢀZhu,ꢀ
J.ꢀMater.ꢀChem.ꢀC,ꢀ2013,ꢀ1,ꢀ7519-7525;ꢀ(b)ꢀL.ꢀGuo,ꢀD.ꢀCao,ꢀ
J.ꢀMater.ꢀChem.ꢀCꢀ2015,ꢀ3,ꢀ8490-8494;ꢀ(c)ꢀD.ꢀMa,ꢀB.ꢀLi,ꢀZ.ꢀ
Cui,ꢀK.ꢀLiu,ꢀC.ꢀChen,ꢀG.ꢀLi,ꢀJ.ꢀHua,ꢀB.ꢀMa,ꢀZ.ꢀShi,ꢀS.ꢀFeng,ꢀ
Appl.ꢀMater.ꢀInt.ꢀ2016,ꢀ8,ꢀ24097-24103.ꢀ
(
e)ꢀ T.ꢀ Sekikawa,ꢀ O.ꢀ Schalk,ꢀ G.ꢀ Wu,ꢀ A.ꢀ E.ꢀ Boguslavskiy,ꢀ A.ꢀ
Stolow,ꢀ J.ꢀ Phys.ꢀ Chem.ꢀ Aꢀ 2013,ꢀ 117,ꢀ 2971−2979;ꢀ (f)ꢀꢀ
Benelhadj,ꢀW.ꢀMuzuzu,ꢀJ.ꢀMassue,ꢀP.ꢀRetailleau,ꢀA.ꢀCharaf-
Eddin,ꢀ A.ꢀ D.ꢀ Laurent,ꢀ D.ꢀ Jacquemin,ꢀ G.ꢀ Ulrich,ꢀ R.ꢀ Ziessel,ꢀ
Chem.ꢀEur.ꢀJꢀ2014,ꢀ20,ꢀ12843-12857;ꢀ(g)ꢀK.ꢀSkonieczny,ꢀJ.ꢀ
Yoo,ꢀ J.ꢀ M.ꢀ Larsen,ꢀ E.ꢀ M.ꢀ Espinoza,ꢀ M.ꢀ Barbasiewicz,ꢀ V.ꢀ I.ꢀ
Vullev,ꢀC.-H.ꢀLee,ꢀD.ꢀT.ꢀGryko,ꢀChem.ꢀEur.ꢀJꢀ2016,ꢀ22,ꢀ7485ꢀ
[
23]ꢀ
(a)ꢀS.ꢀKandambeth,ꢀD.ꢀB.ꢀShinde,ꢀM.ꢀK.ꢀPanda,ꢀB.ꢀLukose,ꢀT.ꢀ
Heine,ꢀR.ꢀBanerjee,ꢀAngew.ꢀChem.ꢀInt.ꢀEd.ꢀ2013,ꢀ52,ꢀ13052ꢀ
-
ꢀ13056;ꢀ(b)ꢀX.ꢀChen,ꢀM.ꢀAddicoat,ꢀE.ꢀJin,ꢀL.ꢀZhai,ꢀH.ꢀXu,ꢀN.ꢀ
Huang,ꢀZ.ꢀGuo,ꢀL.ꢀLiu,ꢀS.ꢀIrle,ꢀD.ꢀJiang,ꢀJ.ꢀAm.ꢀChem.ꢀSoc.ꢀ
015,ꢀ137,ꢀ3241-3247;ꢀ(c)ꢀS.ꢀKandambeth,ꢀV.ꢀVenkatesh,ꢀ
–
7496;ꢀ(h)ꢀP.ꢀSingh,ꢀH.ꢀSingh,ꢀR.ꢀSharma,ꢀG.ꢀBhargava,ꢀS.ꢀ
2
Kumar,ꢀJ.ꢀMater.ꢀChem.ꢀCꢀꢀ2016,ꢀ4,ꢀ11180-11189.ꢀ
(a)ꢀR.ꢀM.ꢀTarkka,ꢀX.ꢀZhang,ꢀS.ꢀA.ꢀJenekhe,ꢀJ.ꢀAm.ꢀChem.ꢀSoc.ꢀ
D.ꢀB.ꢀShinde,ꢀS.ꢀKumari,ꢀA.ꢀHalder,ꢀS.ꢀVerma,ꢀR.ꢀBanerjee,ꢀ
Nat.ꢀCommun.ꢀ2015,ꢀ6,ꢀ6786-6795.ꢀ
[
7]ꢀ
1
996,ꢀ118,ꢀ9438-9439;ꢀ(b)ꢀD.ꢀW.ꢀChang,ꢀS.ꢀKim,ꢀS.ꢀY.ꢀPark,ꢀ
4
ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Page 5 of 6
Jo uP rl ne aa sl eo ꢀ fd Mo ꢀ an to et rꢀ ai ad l jsu sC t hꢀ me am r ig si nt rsyꢀ C
JournalꢀNameꢀ
ꢀCOMMUNICATIONꢀ
[
24]ꢀ
ꢀ
L.ꢀ Prodi,ꢀ F.ꢀ Bolletta,ꢀ M.ꢀ Montalti,ꢀ N.ꢀ Zaccheroni,ꢀ Coord.ꢀ
Chem.ꢀRev.ꢀ2000,ꢀ205,ꢀ59-83.ꢀ
View Article Online
DOI: 10.1039/C7TC00123A
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ5ꢀ
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Journal of Materials Chemistry C
Page 6 of 6
View Article Online
DOI: 10.1039/C7TC00123A
The excited-state intramolecular proton transfer (ESIPT) properties of three tris(N-
salicylideneaniline)-based (TSA) imine-linked porous organic polymers (POPs) were
investigated.
N
NH
O
TSAꢀPOP 1
TSAꢀPOP 2
OH
hν
HO
HO
N
N
TSAꢀPOP 3