Dipolar Ferrocene and Ruthenocene Second-Order Nonlinear Optical Chromophores: A Time-Dependent Density Functional Theory Investigation of Their Absorption Spectra

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dc.authoridBarlow, Stephen/0000-0001-9059-9974|Salman, Seyhan/0000-0002-6124-3706|Salman, Seyhan/0000-0002-6124-3706
dc.authorwosidBarlow, Stephen/ABE-6100-2021
dc.authorwosidSalman, Seyhan/I-1175-2012
dc.authorwosidBredas, Jean-Luc E/A-3431-2008
dc.authorwosidBarlow, Stephen/E-9754-2010
dc.authorwosidMarder, Seth/GRR-9990-2022
dc.authorwosidSalman, Seyhan/F-3154-2015
dc.contributor.authorSalman, Seyhan
dc.contributor.authorBredas, Jean-Luc
dc.contributor.authorMarder, Seth R.
dc.contributor.authorCoropceanu, Veaceslav
dc.contributor.authorBarlow, Stephen
dc.date.accessioned2024-07-18T20:56:56Z
dc.date.available2024-07-18T20:56:56Z
dc.date.issued2013
dc.departmentİstanbul Bilgi Üniversitesien_US
dc.description.abstractThe origin of the two prominent solvatochromic near-UV/visible/near-IR absorptions observed for donor-(pi-bridge)-acceptor chromophores with ferrocene donors has been investigated using TD-DFT methods. Both chromophores with relatively weak (4-nitrophenyl) and strong acceptors (1,3-diethyl-2-thiobarbituric acid and 3-dicyanomethylidene-2,3-dihydrobenzothiophene-1,1-dioxide) were considered, as were ferrocene and octamethylferrocene donors. Computational predictions of optical properties made using the B3PW91 functional were found to be in good agreement with experimental data. The calculations reveal a complex orbital picture that varies from compound to compound, contribution of multiple configurations to some of the important states, and significant contributions from more than one transition to the experimentally observed bands. Natural transition orbitals have been used to gain an understanding of the charge redistribution associated with the transitions. The relatively weak low-energy bands of the ferrocene derivatives were generally found to have both d-d and metal-to-pi-bridge/acceptor charge-transfer character. The stronger higher energy bands were found to be associated with charge transfer from cyclopentadienyl rings and the pi bridge toward the acceptor group. The experimental spectra of ruthenocene chromophores differ significantly from those of the analogous ferrocene chromophores; however, the calculations reproduce the key differences and indicate a similar origin for the contributing transitions.en_US
dc.description.sponsorshipNational Science Foundation [DMR-0120967]en_US
dc.description.sponsorshipWe thank the Science and Technology Program of the National Science Foundation for support (DMR-0120967).en_US
dc.identifier.doi10.1021/om400617d
dc.identifier.endpage6068en_US
dc.identifier.issn0276-7333
dc.identifier.issn1520-6041
dc.identifier.issue20en_US
dc.identifier.scopus2-s2.0-84887115534en_US
dc.identifier.scopusqualityQ1en_US
dc.identifier.startpage6061en_US
dc.identifier.urihttps://doi.org/10.1021/om400617d
dc.identifier.urihttps://hdl.handle.net/11411/8906
dc.identifier.volume32en_US
dc.identifier.wosWOS:000326365900043en_US
dc.identifier.wosqualityQ1en_US
dc.indekslendigikaynakWeb of Scienceen_US
dc.indekslendigikaynakScopusen_US
dc.language.isoenen_US
dc.publisherAmer Chemical Socen_US
dc.relation.ispartofOrganometallicsen_US
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanıen_US
dc.rightsinfo:eu-repo/semantics/closedAccessen_US
dc.subject2nd-Harmonic Generationen_US
dc.subjectQuadratic Hyperpolarizabilitiesen_US
dc.subjectOrganometallic Compoundsen_US
dc.subjectHeterocyclic Acceptorsen_US
dc.subjectConjugated Ferroceneen_US
dc.subjectPoled-Polymeren_US
dc.subjectComplexesen_US
dc.subjectDonoren_US
dc.subjectSystemsen_US
dc.subjectDerivativesen_US
dc.titleDipolar Ferrocene and Ruthenocene Second-Order Nonlinear Optical Chromophores: A Time-Dependent Density Functional Theory Investigation of Their Absorption Spectraen_US
dc.typeArticleen_US

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