杯芳烃类化合物分子识别与分子器件的理论分析-molecular recognition of calixarene compounds and theoretical analysis of molecular devices.docxVIP

AbstractCurrently,molecularrecognitionandsupramoleculardevicesareoneofthehottesttopicsinsupramolecularchemistry.Thecurrentpapersystematicallystudiedthefollowingfourcalixarenecompoundsystemsusingthequantumchemistrymothods:(1)complexationofalkali-metalcationsbyconformationallyrigid,stereoisomericcalix[4]arenecrownethers;(2)computationalinvestigationofanewion-pairreceptorforcalix[4]pyrrole;(3)computationalinvestigationsintonewfluorescencequenchingprocessinducedbycomplexationofalkalimetalion;(4)theoreticalstudyonconformationalfeaturesandcation-bindingpropertiesofadiquinonecalix[4]arene.Firstly,thequantummechanicalstudyofthecone,partial-cone,and1,3-alternate1,3-diethoxy-p-tert-butylcalix[4]crown-5andtheirinteractionwiththealkalimetalcations(Na+,K+,andRb+)hasbeenperformed.Geometries,bindingenergies,andbindingenthalpiesareevaluatedattherestrictedhybridBecke’sthreeparameterexchangefunctional(B3LYP)levelusingstandard6-31Gbasissetandrelativisticeffectivecorepotentials.Theoptimizedgeometricstructuresareusedtoperformnaturalbondorbital(NBO)analysis.Ourcalculationsclearlyshowthatsolvationeffectsstronglyinfluencecationselectivity.1,3-diethoxy-p-tert-butylcalix-[4]crown-5isomerspreferentiallybindNa+,notK+asfoundinaqueousenvironments.However,thecalculatedresultsindicatethatK+selectivityisrecoveredwhenevenafewwatersofhydrationareconsidered.Secondly,theoreticalstudiesofanewion-pairreceptormeso-octamethylcalix[4]pyrrole(OMCP)anditsinteractionswiththehalideanions(F?,Cl?,andBr?)andcesiumhalides(CsF,CsCl,andCsBr)havebeenperformed.Geometries,bindingenergies,andbindingenthalpiesareevaluatedattherestrictedhybridBecke’sthree-parameterexchangefunctional(B3LYP)methodusing6-31+G(d)basissetandrelativisticeffectivecorepotentials.Theoptimizedgeometricstructuresareusedtoperformnaturalbondorbital(NBO)analysis.Theresultsindicatethathydrogenbondinginteractionsaredominantandthehalideanions(F?,Cl?,andBr?)offerloneIIpairelectronstothecontactingσ*(N–H)orσ*(C–H)antibondorbitalsofOMCP.Inaddition,electrostati