极长与极短的铜铜距离-吡唑环三核亚铜配合物亲铜作用本质及发光调控

《极长与极短的铜铜距离-吡唑环三核亚铜配合物亲铜作用本质及发光调控》由会员上传分享，免费在线阅读，更多相关内容在工程资料-天天文库。

1、极长与极短的铜铜距离-毗哇环三核亚铜配合物亲铜作用本质及发光调控郑霁邢立锐李丹暨南大学化学与材料学院汕头大学化学系摘要:本文结合近年来亲金属作用研究领域的进展，针对本课题组在环三核亚铜配合物方而的最新研究成果，讨论了两个铜（I）-铜（I）作用相差悬殊的体系。一是通过构筑具有环三核单元的三棱柱笼状配合物，确认在正堆积模式下即使环三核单元之间亲铜作用极弱依然可以在磷光发射态中产牛强亲铜作用，且通过配体的预留配位点与CU2I2簇连结从而得到自校准大范围发光温度计;二是通过与亲铜作用正交的Br-Br卤键，

2、实现环三核亚铜配合物前所未有的极短铜（I）-铜（I）距离，通过各种电子结构分析方法研究其本质。结果表明即使当铜（I）-铜（1）距离很接近铜的范徳华半径和时，其本质依然为闭壳层作用，而Br-Br作用总为闭壳层作用，且该体系中最强的Br-Br作用很好地休现岀一个Br原子的o穴和另-一个Br原子的负静电势区域的匹配性。关键词：亲铜作用;止堆积;磷光发射态;卤键;约化密度梯度;分子中的原子的量子理论；作者简介：LIDan,Ema订：danli@jnu.edu.cn;Tel:+86-20-85221697.

3、收稿日期：Apr订26,2017基金：国家重点基础研究发展计划（973）（2012CB821706,2013CB834803）ExtremeLongandExtremeShortCu-CuDistances:NatureofCuprophilicityandLuminescenceModificationinCu(I)-basedCyclicTrinuclearComplexesZHENGJiXINGLi—RuiL[DanCollegeofChemistryandMaterialsScience,

4、JinanUniversity;DepartmentofChemistry,ShantouUniversity;Abstract：Thismonographfocusesonrecentprogressintheresearchfieldofmetallophilicity,incombinationofourlatestresultsonCu(I)-basedcyclictrinuclearcomplexes,mainlydiscussingtwoexampleswithverydifferen

5、tcuprophilicity.Oneisbyconstructingtriangularcoordinationprismsbearingcyclictrinuclearunits,confirmingthatstrongcuprophilicattractioncouldexistinthephosphorescentemissivestateunderfrontalpackingmodeevenwhenthecuprophilicityisextremeweakatgroundstate,a

6、ndbycoordinationwithaCu2I2clusterwithanadditionalcoordinatesiteintheligand,sothataself-calibratedwide~rangeluminescentmolecularthermometerwasobtained.TheotheristherealizationoftheshortestCu-CudistanccsofarinthisfieldbyBr-Brhalogenbondorthogonaltocupro

7、philicity,followedbytheinvestigationusingseveralkindsofelectronicstructureanalysis.TheresultshowsthatevenwhentheCu-CudistanceapproachesthevanderWaalsradiisumofCu,itsnatureisstillclosed-shellinteraction,whichisalsothenatureofallBr-Brinteraction,emdthes

8、trongestBr-Brintcractioninthissystemdisplaysgoodmatchingbetweentheo-holeofaBratomandthebeltofnegativepotentialofanotherBratom.Keyword：Cuprophi1icity;Frontalpacking;Phosphorescentemissivestate;Halogenbond;Reduceddensitygradient;Quantumtheoryofa