title: Drastic tuning of the photonic properties of "(push-pull)n" trans-bis(ethynyl)bis(tributylphosphine)platinum(II)-containing polymers.
abstract: 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.
authors.affiliation: Département de chimie, Université de Sherbrooke, Sherbrooke, PQ, Canada, J1K 2R1.
authors.forename: Xiaorong
authors.initials: X
authors.lastname: Wang
authors.forename: Daniel
authors.initials: D
authors.lastname: Fortin
authors.forename: Gessie
authors.initials: G
authors.lastname: Brisard
authors.forename: Pierre D
authors.initials: PD
authors.lastname: Harvey
mesh_terms: D015502:Absorptiometry, Photon; D056831:Coordination Complexes / Q000737:chemistry; D018360:Crystallography, X-Ray; D008968:Molecular Conformation; D010720:Phosphines / Q000737:chemistry*; D017785:Photons; D010984:Platinum / Q000737:chemistry*; D011108:Polymers / Q000138:chemical synthesis / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D056831:Coordination Complexes; D010720:Phosphines; D011108:Polymers; C043255:tri-n-butylphosphine; D010984:Platinum
keywords: anthraquinone; bis(ethynyl)platinum(II); charge transfer; conjugated polymer; electrochemistry; electronic communication