修飾鋅卟啉軸向配位反應熱力學及量化計算理論研究.pdf

1、南開大學碩士學位論文修飾鋅卟啉軸向配位反應熱力學及量化計算理論研究姓名：袁偉申請學位級別：碩士專業(yè)：物理化學指導教師：朱志昂2001.5.1一壘曼!!墾壘竺!—————————————————————————————●—————_—————●———————————一一ABSTRACTMetalloporphyrinsareofgreatsignificanceinthefieldofboinorganicchemistry，C00rdi

2、nationchemistryandhost—guestchemistry。Studiesonmetalloporphyrinshayealwaysbeenafocusfort11eresearchersintheworld。Theyarerelatedtomanyfieldsofmodemchemistry。Molecularrecognitionandaxiscoordinationofmetalloporphyrinshasbee

3、nstudiedinthisthesis，andthetooloftheoreticchemistryhasbeenperformedtodeeplyprobethisfieldaswell。Themaincontentisshownasfollows：1Freeandzincporphyrinsmodifiedbychloroacetylchlorid，andaminoacidderivativesweresynthesizedand

4、characterizedbyUVvis，。HNMR，IR，spectrum。2Themolecularrecognitionofimidazolesbymodifiedzincporphydnswasstudied。ThebindingconstantsbetweenhostandguestmoleculesweremeasuredbythemethodofUVvisspectrophotometrictitration。Affect

5、factorsofbindingconstantswerediscussed，whichincludethesterieconfigurationofhostmolecules，thevolumeandpositionofguest‘Ssubstitutinggroups，andtemperature。Thethermodynamicpropertiesandenthalpyentropycompensationwereconsider

6、ed。TherelationshipbetweenelectronicstructureandbindingabilitiesofguestmoleculesWasdecidedbythemethodsofquantumchemistry；Theminimalenergyconformationsofhostguestsystemswereobtained。3Inordertogettheconditionsofasymmetricca

7、talyticoxidationofunfunctionalizedolefinsbymetalloporphyrins；wehaveresearchthereactionofstyreneoxidationcatalyzedbyFeTPPCIwhichhadbeensynthesizedbyowngroup。Theresearchshowedthatitprovidessomeusefu／experieneeforthenextste