修飾鋅卟啉軸向配位反應(yīng)熱力學(xué)及量化計算理論研究.pdf

1、南開大學(xué)碩士學(xué)位論文修飾鋅卟啉軸向配位反應(yīng)熱力學(xué)及量化計算理論研究姓名：袁偉申請學(xué)位級別：碩士專業(yè)：物理化學(xué)指導(dǎo)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