Three pillared-layered inorganic–organic hybrid polymers with efficient luminescence 2017 Xi Liu.pdf

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Threepillared-layeredinorganic–organichybrid
polymerswithefficientluminescence†
Citethis:RSCAdv.,2017,7,40632
XiLiu,*ZhenZhao,Chun-HaiWang,ShanFuandKun-LinHuang
00
Threepillared-layeredinorganic–organichybridpolymers,namely,[Cu2(4,4-Hbpt)(SCN)2]n(1),[Cd(4,4-
0
Hbpt)(SCN)2]n(2),and[Cd(4,4-Hbpt)(SCN)2$CH3CN]n(3)
10
allthreecomplexes,thereexist2-Dneutralwave-likedmetalthiocyanatelayers(for1,[Cu2(SCN)2]n,
0
andfor2and3,[Cd(SCN)2]n)with(4,4)topology,whicharefurtherconnectedbybidentate4,4-Hbpt
ligandstoform3-
thermogravimetricanalysesindicatethatthethreecomplexesaregoodcandidatesasluminescent
Received26thJune2017
-layeredinorganic–
Accepted15thAugust2017
organichybridpolymersconstructedwithlayeredd10metalthiocyanatelayersandconjugatedorganic
DOI:,aswellasthediscoveryofnewpatternsofcrystallizationat
-advancesthecrystalengineeringlevel.
CreativeCommonsAttribution-.
Introductioninterestinviewoftheirremarkablephotophysicalandphoto-
chemicalpropertiesbasedontheird10electroniccongura-
Inorganic–OrganicHybridPolymers(IOHPs)constructedfromtions,5whichshouldleadtointerestingnewfunctional
À
inorganicsolidsandfunctionalorganicligandshaveattractedluminescentmaterials.(2)SCNisahighlyversatileambi-

applicationsintheeldsofluminescentdevices,electricalionsthrougheitherthenitrogenorthesulfuratom,orboth,
conductivity,molecularmagnetism,catalysis,moleculargivingrisetolinkageisomersorframeworksofvarieddimen-
Thisarticleislicensedunderaa
absorption,andhost–(3)recentstudies3onIOHPscontaininglayeredd10
advantageouspropertiesofinorganic,organic,andpolymericmetalthiocyanateshaveshotlightontheirinterestingphoto-
materials,andalsoallowconcomitantbutseparatemolecularluminescenceproperties,whilehowtoobtainthesecomplexes
:46:ctopologiesanddesirableluminescentproperties,
partsasspacers,controllers,andtemplatesatthemolecularandsortouttherelationshipbetweenthestructuresandphys-
.
importantbecausethepreferredbackbonesofinorganicpartsOntheotherhand,theappropriatedesignorselectionof
maydeterminethetopologiesofthecoordinationframework,organicligandsisundoubtedlyanotherkeyroleinassembling
especiallyforstructurescontainingvarioussimilarorganicIOHPswithspecictopologiesanddesirableproperties.
,layeredConjugatedorganicspacers,forexamples,3,5-bis(n-pyridyl)-
transitionmetalthiocyanates2,3especiallyd10metalthiocya-1,2,4-triazolesaretypicaldipyridylligandswithaslightlybent
,andattractconsiderableinterestinconstructionof
mainreasonsthatdriveustofocusonthed10metalthiocya-,conju-
natesasinorganicpartsinIOHPs:(1)asapartofourcontinuinggatedorganicligandsareusuallypossessinggoodpotential
investigations4onluminescentd10metalcoordinationpoly-abilitytoenhancephotoelectrontransferduetotheirextended
mers,theincorporationofd10metalsinIOHPsisofgreatp-,thecombination
ofinorganiclayersofd10metalthiocyanatesandconjugated
organicligandsmayleadtoanovelclassofpillared-layered
ChongqingKeyLaboratoryofInorganicFunctionalMaterials,CollegeofChemistry,IOHPswithspecialstructuralarchitecturesandexcellent
ChongqingNormalUniversity,Chongqing401331,-mail:******@,d10metalthiocyanatesand3,5-bis(4-
;Fax:+86-023-65362777;Tel:+86-023-65910310
pyridyl)-1,2,4-triazole(4,40-Hbpt)wereselectedtoassemble
†Electronicsupplementaryinformation(ESI)available:Additionalplotsofthe0
structures;theoreticalapproachmethodology,computationalthreenovelpillared-layeredIOHPs,namely,[Cu2(4,4-
00
description/explanation;TGAcurves;PXRDdiagrams;IRspectra;Hbpt)(SCN)2]n(1),[Cd(4,4-Hbpt)(SCN)2]n(2),and[Cd(4,4-
10
crystallographicdatafor1,,1538779andHbpt)(SCN)2$CH3CN]n(3)withneutralwave-likedmetal
,
DOI:
40632|RSCAdv.,2017,7,40632–40639Thisjournalis©TheRoyalSocietyofChemistry2017
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PaperRSCAdvances
0
crystalstructures,photoluminescentproperties,therelation-Synthesisof[Cd(4,4-Hbpt)(SCN)2$CH3CN]n(3)
shipsbetweenthestructuresandphotoluminescence,thermal
SuitableamountofNH4SCNwereaddedtoanaqueous
stabilitiesofthethreecomplexeswerealsoinvestigated.
suspension(2mL)ofCdCO3(,),andthe
mixturewerestirreduntilCdCO3solidwerealmostdissolved.
ExperimentalsectionTheresultingsolutionwastransferredtoaglasstube,andthen
wascarefullyaddedabufferlayerofCH3CN(1mL).ACH3CN
0
Materialsandinstrumentationsolution(1mL)of4,4-Hbpt$2H2O(,)was
Theligand3,5-bis(4-pyridyl)-1,2,4--brown
ff
-diusionofthe
0
wereobtainedfromcommercialsourcesandwereusedwithoutreactantsinvedayswith46%yield(basedon4,4-Hbpt).Anal.
furtherpuri-():C,;H,;N,.
À1
À1n
pelletsonaFT-IR8400S(CE)intherange4000–,H,Found:C,;H,;N,-IR(KBrpellet,/cm):
andNelementalanalyseswerecarriedoutonaVarioELIII3443(b,s),2104(s),2075(s),1994(m),1618(m),1587(m),1547(m),
-raypowderdiffractiondatawererecorded1524(w),1495(w),1466(w),1423(s),1369(m),1315(w),1219(w),
a¼˚1140(w),1061(w),1013(w),840(w),758(m),729(s),507(w),
withCuKradiation()onaXRD-6100withascanÀ
À1n^
(w).(CN)vibrationofSCNandCH3CNanions:2104(s),
onaHENVEN-HJHCT-3thermoanalyzerataheatingrateof2075(s).
À
10

analysesweremeasuredonaPerkin-ElmerLS55uorescenceX-raysinglecrystalstructuredeterminations
spectrometer.
Suitablesinglecrystalsof1,2and3werecarefullyselected
underanopticalmicroscopeandgluedtothinglass
CreativeCommonsAttribution-
Synthesisof[Cu2(4,4-Hbpt)(SCN)2]n(1)collectionswereperformedonaRigakuMercuryCCDdirac-
tometerequippedwithagraphitemonochromatedMoKa
MethodA
radiation(l¼)˚
,40-Hbpt$2HO(,
2collectedwithanu-scantechniqueandreducedbyCrystalClear
)inethanol(2mL)waslayeredoverasolutionof

CuSCN(,)insaturatedKSCNwatersolution
andrenedbyfull--
(2mL).Overthreedays,redcrystalswereobtainedin55%yield
hydrogenatomswerelocatedbydifferenceFouriermapsand
(basedon4,40-Hbpt).():C,
149272subjectedtoanisotropicre
;H,;N,:C,;H,;N,-IR
À-
Thisarticleislicensedundera(KBrpellet,n/cm):2120(s),1582(w),1543(w),1491(w),1422(s),
tionswereperformedbytheSiemensSHELXTLversion
1366(m),1140(m),1059(m),1013(w),835(m),754(s),721(m),11
À5packageofcrystallographicso
532(m),494(w).n(C^N)vibrationofSCNanions:2120(s).
andstructuralrenementsfor1,2and3aresummarizedin
MethodB
:46:
,40-Hbpt$2HO

(,),Cu(NO)$3HO(,),
322atomdisplacementparametersaregivenasESI.†
KSCN(,)andCH3CN/H2O(3mL,v/v¼1:2)
wassealedina25mLTeon-linedstainless-
reactorwasheldat80or120Cfor3days,andthenwascooling
ÀResultsanddiscussion
toroomtemperatureatarateof10
wereobtainedin60%yield(basedon4,40-Hbpt).Synthesisandgeneralcharacterization
Asdescribedabove,complex1couldbeobtainedbytwo
ff
0methods,namely,layerdiusionmethodandhydrothermal
Synthesisof[Cd(4,4-Hbpt)(SCN)2]n(2),theredcrystalsobtainedvia
$
Anaqueoussolution(2mL)ofCd(NO3)24H2O(,hydrothermalsynthesiscouldnotbedeterminedbyX-raysingle
),KSCN(,)inaglasstubewascrystalanalysisduetotheirpoorcrystallinity,whichwere
carefullyaddedabufferlayerofCH3CH2OH(1mL).Anethanolconrmedtobethesameasthoseweresynthesizedvialayer
0
solution(2mL)of4,4-Hbpt$2H2O(,)wasdiffusionmethod,byelementalanalyses,IRspectroscopy,and
-,thebufferlayerofCH3CH2OH
rhombuscrystalsof2wereobtainedoninter-diffusionofthesolventisimportantsinceitcouldeffectivelypreventthe
reactantsinthreedayswith50%yield(basedon4,40-Hbpt).,the
():C,;H,;N,
À12À
Found:C,;H,;N,-IR(KBrpellet,n/cm):CdCO3andcomplexationconstantofCd(SCN)4inaqueous
2104(s),1587(w),1547(w),1491(w),1422(s),1368(m),1142(m),solutionatroomtemperature,themixtureofNH4SCNand
1063(m),1011(w),849(m),756(m),727(s),507(m),455(w).CdCO3inaqueoussolutionshouldbelteredbeforetransferred
À
n(C^N)vibrationofSCNanions:2104(s).toaglasstube.
Thisjournalis©TheRoyalSocietyofChemistry2017RSCAdv.,2017,7,40632–40639|40633
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Table1Crystalandstructurerefinementdatafor1,2and3a
Complexes123
FormulaC14H9Cu2N7S2C14H9CdN7S2C16H12CdN8S2
Temperature(K)293(2)293(2)293(2)

Wavelength(A)˚
CrystalsystemMonoclinicMonoclinicMonoclinic
SpacegroupC2/cC2/cP2(1)/c
Unitcelldimensions,a(A),˚b(A),˚c(A)˚(3),(2),(3)(4),(1),(1)(2),(3),(4)
a(deg.)909090
b(deg.)(8)(6)(5)
g(deg.)909090
V(A˚3)(6)(4)(9)
Z444
À3
Dcalc(gcm)
F(000)928888976
À
Absorptioncoefficient(mm1)
Reectionscollected/unique(Rint)7431/1470()7285/2260()27657/3760()
Data/restraints/parameters1470/0/1141997/0/1113760/12/244
¼¼¼¼¼¼
Rindex(I>2s(I)),,,
Goodness-of-
À
Largestdifferenceinpeakandhole(eA˚3)ÀÀÀ

PPX21=2
a222
R1¼[||F0|À|Fc||/|F0|],wR2¼F0ÀFcjFWj.
WW
CreativeCommonsAttribution-.

Table2Selectedbonddistances(A)˚andangles()forcomplexes1,2Inadditiontothecharacteristicvibrationbandsofthe
aÀÀ
and3aromaticheterocyclicat1400–1625cm1,near1367cm1(s),
ÀÀ
around1420cm1,strongadsorptionbandsofSCNligands
Complexes1À
appearatabout2120,2104,2104cm1for1,2and3respec-
Cu(1)–N(1A)(3)N(1A)–Cu(1)–S(1)(9),forbulksamplesof1,2and3,thephase
Cu(1)–N(11)(3)N(11)–Cu(1)–S(1B)(9)purityisconrmedbycomparingtheirPXRDdatawiththe
–––
Cu(1)S(1)(1)N(1A)Cu(1)N(11)(1)simulateddatafromtheirCIFles,asshowninESI(–S9,
Cu(1)–S(1B)(1)S(1)–Cu(1)–S(1B)(3)
ThisarticleislicensedunderaESI†).
S(1)–C(1)(3)C(1)–S(1)–Cu(1)(1)
N(1)–C(1)(4)C(1)–N(1)–Cu(1C)(3)
Cu(1)–Cu(1B)(1)N(1)–C(1)–S(1)(3)
0
Structureof[Cu2(4,4-Hbpt)(SCN)2]n(1)
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