structural polymorphism and photoluminescence - university at

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1、Cu(I)Wires:StructuralPolymorphismandPhotoluminescencebyCristinaDubceacScientificadvisor:Prof.MarinaA.PetrukhinaAnHonorsThesisSubmittedtotheDepartmentofChemistryUniversityatAlbany,StateUniversityofNewYorkInpartialFulfillmentoftheRequirementsforAnHonorsBachelorofScienceDegreeinChemistr

2、yMay201155ACKNOLEDGEMENTSIwouldliketoexpressmysincerestthanksandgratitudetomyadvisorDr.MarinaA.Petrukhinafornotonlybeingagreatmentor,butalsoforprovidingmewithmultidisciplinaryandcollaborativeenvironmentstoconductresearch.IappreciatethetimeandeffortthatProf.Petrukhinaspentinrevisingmy

3、work.IwouldliketotakethisopportunitytothanktheChemistryDepartmentChairProf.PaulJ.Toscanoforhisvaluableinstructionsandadviceduringmystudy.AspecialthankyoutothePh.D.studentOleksandrHietsoiandtoDr.AlexanderS.Filatovforcrystalstructuresdeterminationandcharacterization.Iwouldalsoliketotha

4、nkthegraduatestudentsfromprofessorPetrukhina’slabatUniversityatAlbanyfortheirhelpduringthetimespentinthelabworkingonthisproject.551.ABSTRACTMetalwiresarealineararrangementofmetalcentersthatconductelectricalcurrent.Linearpolynuclearmetalclustersareofgreatimportanceforthedesignofmetal-

5、richnano-materialsandthedevelopmentoftheoriesdescribingmetal-metalbonds.Theoreticalworkonmetalstringsisvaluableinunderstandingtheirpropertiesanddiscoveringtheirpotentialapplicationsasmolecularwires.Linearmetalatomchainscanbeligandsupportedorunsupported.Theanionsofpolypyridylamineshav

6、ebeenusedextensivelytosupportlinearmetalchains.However,duetochallengesinvolvingthesynthesisoftheseligands,thelongestmetalchainreportedcontainsninemetalatoms.Examplesofunsupportedextendedcopperchainsemphasizethecrucialroleofcuprophilicinteractionsinsupportingthesestrings.AlsobasedonCu

7、×××Cucontactsaretheinfinitehelicalarrangementsofcarboxylatebridgedcopper(I)ionsinCu(I)pivalateandCu(I)3,5-bis(trifluoromethyl)benzoate.Amongcarboxylates,the2,4,6-triisopropylbenzoateligandisknowntobesufficientlybulkytopreventself-associationofdinuclearpaddlewheelunits.Therefore,itwas

8、selectedinth