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dc.contributorWichita State University. Department of Chemistryen_US
dc.contributor.authorChitta, Raghuen_US
dc.contributor.authorRogers, Lisa M.en_US
dc.contributor.authorWanklyn, Amberen_US
dc.contributor.authorKarr, Paul A.en_US
dc.contributor.authorKahol, Pawan K.en_US
dc.contributor.authorZandler, Melvin E.en_US
dc.contributor.authorD'Souza, Francisen_US
dc.date.accessioned2012-02-06T17:17:14Z
dc.date.available2012-02-06T17:17:14Z
dc.date.issued2004-11-01en_US
dc.identifier15500335en_US
dc.identifier0366543en_US
dc.identifierGM 59038en_US
dc.identifier.citationInorganic chemistry. 2004 Nov 1; 43(22): 6969-78.en_US
dc.identifier.issn0020-1669en_US
dc.identifier.urihttp://dx.doi.org/10.1021/ic0497228en_US
dc.identifier.urihttp://hdl.handle.net/10057/4401
dc.descriptionClick on the DOI link below to access the article (may not be free).en_US
dc.description.abstractThe effect on the electrochemical oxidation and reduction potentials of 5,10,15,20-tetrakis(benzo-15-crown-5)porphyrin (TCP) and its metal derivatives (MTCP; M = Mg(II), VO(IV), Co(II), Ni(II), Cu(II), Zn(II), Pd(II), Ag(II)) upon potassium ion induced dimerization of the porphyrins was systematically performed in benzonitrile containing 0.1 M (TBA)ClO(4) by differential pulse voltammetry technique. The HOMO--LUMO energy level diagram constructed from the electrochemical data revealed destabilization of the HOMO level and stabilization of the LUMO level upon dimer formation while such a perturbation was larger for the HOMO level than the LUMO level. The geometry and electronic structure of a representative ZnTCP and its dimer, K(4)(ZnTCP)(2), were evaluated by the ab initio B3LYP method utilizing a mixed basis set of 3-21G(*) for Zn, K, O, and N and STO-3G for C and H. The inter-porphyrin ring distance of the dimer calculated from the optimized geometry agreed with the spectroscopically determined one, and the calculated HOMO and LUMO frontier orbitals revealed delocalization on both of the porphyrins rings. The metal-metal distances calculated from the triplet ESR spectra of the K(+) induced porphyrin dimers bearing paramagnetic metal ions in the cavity followed the trend Cu--Cu < VO--VO < Ag--Ag. However, the spectral shifts resulting from the exciton coupling of the interacting porphyrin pi-systems revealed no specific trend with respect to the metal ion in the porphyrin cavity. Additionally, linear trends in the electrochemically measured HOMO--LUMO gap and the energy corresponding to the most intense visible band of both MTCP and K(4)(MTCP)(2) were observed. A reduced HOMO--LUMO gap predicted for the dimer by B3LYP/(3-21G(), STO-3G) calculations was confirmed by the results of optical absorption and electrochemical studies.en_US
dc.description.sponsorshipNIGMS NIH HHSen_US
dc.format.extent6969-78en_US
dc.language.isoengen_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.ispartofseriesInorganic chemistryen_US
dc.relation.ispartofseriesInorg Chemen_US
dc.sourceNLMen_US
dc.subjectResearch Support, Non-U.S. Gov'ten_US
dc.subjectResearch Support, U.S. Gov't, Non-P.H.S.en_US
dc.subjectResearch Support, U.S. Gov't, P.H.S.en_US
dc.subject.meshAlgorithmsen_US
dc.subject.meshCobalt/chemistryen_US
dc.subject.meshCopper/chemistryen_US
dc.subject.meshCrown Ethers/chemistryen_US
dc.subject.meshElectrochemistryen_US
dc.subject.meshMagnesium/chemistryen_US
dc.subject.meshMetalloporphyrins/chemical synthesisen_US
dc.subject.meshMolecular Conformationen_US
dc.subject.meshMolecular Structureen_US
dc.subject.meshNickel/chemistryen_US
dc.subject.meshPalladium/chemistryen_US
dc.subject.meshSilver/chemistryen_US
dc.subject.meshVanadium/chemistryen_US
dc.subject.meshZinc/chemistryen_US
dc.subject.meshMetalloporphyrins/chemistryen_US
dc.titleElectrochemical, spectral, and computational studies of metalloporphyrin dimers formed by cation complexation of crown ether cavitiesen_US
dc.typeArticleen_US
dc.coverage.spacialUnited Statesen_US
dc.description.versionpeer revieweden_US
dc.rights.holderCopyright © 2004 American Chemical Societyen_US


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