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• W2023762417 abstract "The spectroscopic and electrochemical properties of two series of some [Pt(ĈN)XY]z complexes are studied where (ĈN) is cyclometalated 2-phenyl-pyridinate, Ppy−, and 2-(2-thienyl)pyridinate, Tpy−; X and Y represent various monodentate and bidentate ligands: Cl−, CN−, CO, (Mor)3P=trismorpholinophosphine, Bpy=2,2-bipyridine, Phen=1,10-phenanthroline, En=ethylenediamine, Edp=1,2-bis(diphenylphosphino)ethane, Etdp=1,2-bis(diphenylphosphino)ethene, Edt=1,2-bis(phenylthio)ethane, Mnt2−=1,2dicyano-1,2-ethylenedithiolate. The lowest excited state in the [Pt(Ppy)XY]+ complexes with an unsaturated ligand, (NN) being Bipy and Phen, is assigned to a 3MLCT {d(Pt)−π∗(NN)} transition, while for the Tpy− complexes it corresponds to a 3{d(Pt)−π*(ĈN)} transition. The lowest excited state of the [Pt(ĈN)Mnt]− complexes is assigned to a 3{p(S)/d(Pt)−π∗Mnt)} transition. In the related complexes, in which a saturated chelating ligand replaces the unsaturated one, (NN)En, (SS)Edt, (PP) Edp, and in Pt(ĈN)(P(Mor)3)Cl, Pt(ĈN)COCl, [Pt(ĈN)(CN)2]−, [Pt(ĈN)Cl2]− the lowest excited state is assigned to a 3{d(Pt)−π∗(ĈN)} transition. When replacing the cyclometalating ligand Ppy− with Tpy− the 3MLCT {d(Pt)−π∗(ĈN)} absorption and emission bands are red shifted by ca. 3000 cm−1. The redox potentials, however, are very similar and depend only on the additional ligands X and Y showing the linear relationship relative to Lever's electrochemical parameters. The values of the calculated radiative rate constants are sensitive both to the identity of the X,Y ligands (Edp<Edt<(CN−,CN−)<En<((Mor)3P,Cl−)<(CO,Cl−)<(Cl−,Cl−)) and the (ĈN) ligands (Tpy−<Ppy−). This effect is suggested to be due to a reduction in the amount of charge transfer to the (ĈN) ligand induced by an increase in π-back-bonding to the X,Y-ligands. The photochemical activity of this class of complexes in electron transfer reactions as well as in ground state quenching has been demonstrated." @default.
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• W2023762417 date "1997-03-01" @default.
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• W2023762417 title "Photophysics, photochemistry and electrochemistry of mixed-ligand platinum(II) complexes with 2-phenylpyridine and 2-(2′-thienyl)pyridine as cyclometalating ligands" @default.
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• W2023762417 doi "https://doi.org/10.1016/s0010-8545(96)01300-8" @default.
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