Macromolecular Rapid Communications, Vol.35, No.10, 992-997, 2014
Drastic Tuning of the Photonic Properties of "(Push-Pull)(n)" trans -Bis( ethynyl) bis( Tributylphosphine) Platinum( II)- Containing Polymers
The trans-Pt(PBu3)(2)Cl-2 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 ,* T2S0 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, QN(2); anthraquinone diimine, AQN(2)), for which the CT T1S0 emission is silent, has been completely annihilated and replaced by a red-shifted T1S0 emission in 1 and 2a, which arise from a triplet charge transfer excited state [Pt]AQ.