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  • Title: Photophysics of platinum tetrayne oligomers: delocalization of triplet exciton.
    Author: Li Y, Winkel RW, Weisbach N, Gladysz JA, Schanze KS.
    Journal: J Phys Chem A; 2014 Nov 13; 118(45):10333-9. PubMed ID: 24814902.
    Abstract:
    A series of platinum tetrayne oligomers, all-trans-Cl-Pt(P2)-[(C≡C)4-Pt(P2)]n-Cl, where P = tri(p-tolyl)phosphine and n = 1-3, was subjected to a detailed photophysical investigation. The photoluminescence of each oligomer at low temperature (T < 140 K) in a 2-methyltetrahydrofuran (Me-THF) glass features an intense and narrow 0-0 phosphorescence band accompanied by a vibronic progression of sub-bands separated by ca. 2100 cm(-1). The emission arises from a (3)π,π* triplet state concentrated on the (C≡C)4 carbon chain and the vibronic progression originates from coupling of the excitation to the ν(C≡C) stretch. All of the experimental data including ambient temperature absorption, low-temperature photoluminescence, and ambient temperature transient absorption spectroscopy provide clear evidence that the triplet state is localized on a chromophore consisting of approximately two -[(C≡C)4-Pt(P2)]- repeat units. Density functional theory calculations support the hypothesis that the triplet-triplet absorption arises from transitions that are delocalized over two repeat units.
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