The trans-Pt(PBu3)2 Cl2 complex reacts with 1 equiv. of 2,6-diethynyl-AQ and 2 equiv. of 2-ethynyl-AQ (AQ = anthraquinone) to form the polymer (trans-Pt(2,6-diethynyl-AQ)2 (PBu3)2)n, 1, and the model compounds, 2, trans-Pt(PBu3)2 (2-ethynyl-AQ)2 (in a 20:1 ratio as trans-(2a) and cis-(2b) rotational isomers), respectively. These redox-active and luminescent materials have been characterized by gel permeation chromatography, thermal gravimetric analysis, X-ray crystallography, electrochemistry, photophysics, and DFT computations (B3LYP). The typical π,π* T2 → S0 phosphorescence centered on the trans-Pt(PBu3)2 (aryl)2 chromophore, [Pt], generally encountered for the analogous polymers (trans-Pt(PBu3)2 (aryl)2-acceptor)n (acceptor = quinonediimine, QN2; anthraquinone diimine, AQN2), for which the CT T1 → S0 emission is silent, has been completely annihilated and replaced by a red-shifted T1 → S0 emission in 1 and 2a, which arise from a triplet charge transfer excited state [Pt]→ AQ.
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