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Radical Ion States of Platinum Acetylide Oligomers
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Abstract
The ion radicals of two series of platinum acetylide oligomers have been subjected to study by electrochemical and pulse radiolysis/transient absorption methods. One series of oligomers, Ptn, has the general structure Ph
C
C[Pt(PBu3)2CC(1,4-Ph)CC]nPt(PBu3)2CCPh (where x = 0−4, Ph = phenyl and 1,4-Ph = 1,4-phenylene). The second series of oligomers, Pt4Tn, contain a thiophene oligomer core, CC(2,5-Th)nCC (where n = 1−3 and 2,5-Th = 2,5-thienylene), capped on both ends with Pt(PBu3)2CC(1,4-Ph)CCPt(PBu3)2CCPh segments. Electrochemical studies reveal that all of the oligomers feature reversible or quasi-reversible one-electron oxidation at potentials less than 1 V versus SCE. These oxidations are assigned to the formation of radical cations on the platinum acetylide chains. For the longer oligomers multiple, reversible one-electron waves are observed at potentials less than 1 V, indicating that multiple positive polarons can be produced on the oligomers. Pulse-radiolysis/transient absorption spectroscopy has been used to study the spectra and dynamics of the cation and anion radical states of the oligomers in dichloroethane and tetrahydrofuran solutions, respectively. All of the ion radicals exhibit two allowed absorption bands: one in the visible region and the second in the near-infrared region. The ion radical spectra shift with oligomer length, suggesting that the polarons are delocalized to some extent on the platinum acetylide chains. Analysis of the electrochemical and pulse radiolysis data combined with the density functional theory calculations on model ion radicals provides insight into the electronic structure of the positive and negative ion radical states of the oligomers. A key conclusion of the work is that the polaron states are concentrated on relatively short oligomer segments.
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This article has been cited by 6 ACS Journal articles (5 most recent appear below).
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Jonas Sjöqvist, Mathieu Linares and Patrick NormanThe Journal of Physical Chemistry A2010 114 (14), 4981-4987Platinum(II) and phosphine MM3 force field parameters are derived from fits to the ground state potential energy surface at the level of Kohn−Sham density functional theory with employment of the B3LYP exchange-correlation functional. The parametrization ...
Energy Transfers in Monomers, Dimers, and Trimers of Zinc(II) and Palladium(II) Porphyrins Bridged by Rigid Pt-Containing Conjugated Organometallic Spacers
Diana Bellows, Shawkat M. Aly, Claude P. Gros, Maya El Ojaimi, Jean-Michel Barbe, Roger Guilard and Pierre D. HarveyInorganic Chemistry2009 48 (16), 7613-7629Energy Transfers in Monomers, Dimers, and Trimers of Zinc(II) and Palladium(II) Porphyrins Bridged by Rigid Pt-Containing Conjugated Organometallic Spacers
Diana Bellows, Shawkat M. Aly, Claude P. Gros, Maya El Ojaimi, Jean-Michel Barbe, Roger Guilard and Pierre D. HarveyInorganic Chemistry2009 48 (16), 7613-7629A series of linear monomers (spacer−M(P)), dimers (M(P)−spacer−M′(P)), and trimers (M(P)−spacer−M′(P)−spacer−M(P)) of spacer/metalloporphyrin systems (M′ = Zn, M = Zn, Pd, P = porphyrin, and spacer = trans-C6H4C≡CPtL2C≡CC6H4- (L = PEt3)) including mixed ...
Synthesis of Monodisperse Platinum Acetylide Oligomers End-Capped with Naphthalene Diimide Units
Julia M. Keller and Kirk S. SchanzeOrganometallics2009 28 (14), 4210-4216Synthesis of Monodisperse Platinum Acetylide Oligomers End-Capped with Naphthalene Diimide Units
Julia M. Keller and Kirk S. SchanzeOrganometallics2009 28 (14), 4210-4216We report the synthesis and structural characterization of a series of monodisperse platinum acetylide oligomers with the general structure NDI-[Ph−C≡C−Pt(PBu3)2−C≡C−]n−Ph−NDI, where n = 2, 3, 6, or 10, Ph = 1,4-phenylene, NDI is a substituted 1,4,5,8-...
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History
- Published In Issue September 20, 2007
- Received May 15, 2007
Revised July 2, 2007
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