Fourfold Alkoxy-Substituted [2.2.2]Paracyclophane-1,9,17-trienes-ROMP into PPVs with Unusual Topologies

• Published in: Macromolecular rapid communications. Vol. 35; no. 24; pp. 2096 - 2100
• Main Authors: Mäker, Dominic, Bunz, Uwe H. F.
• Format: Journal Article
• Language: English
• Published: Weinheim Blackwell Publishing Ltd 01-12-2014; Wiley; Wiley Subscription Services, Inc
• Subjects: Alcohols - chemistry; Applied sciences; conjugated polymers; cyclophanetrienes; Decomposition reactions; Electrochemical Techniques; Electrons; Ethers, Cyclic - chemistry; Exact sciences and technology; Fluorescence; Light; metathesis; Organic polymers; Physicochemistry of polymers; Polymerization; Polymers with particular properties; Polyphenylene vinylene; Polyvinyls - chemical synthesis; Polyvinyls - chemistry; PPV; Preparation, kinetics, thermodynamics, mechanism and catalysts; Ring opening; ROMP; Solutions; Spectroscopy; Spectrum Analysis; Synthesis; Voltammetry; Ring opening polymerization; Phenylenevinylene derivative copolymer; ROMP; Fluorescence; Complex catalyst polymerization; Experimental study; Amorphous copolymer; cyclophanetrienes; Electrochemical properties; Conjugated copolymer; Metathesis polymerization; metathesis; Optical properties; Preparation; PPV; Cyclophane; Phenylenevinylene copolymer; Optical absorption; conjugated polymers
• ISSN: 1022-1336; 1521-3927
• DOI: 10.1002/marc.201400515

The synthesis of two 4,7,12,15‐tetrakisalkoxy‐substituted [2.2.2]‐paracyclophane‐1,9,17‐trienes and their polymerization employing ring opening metathesis polymerization (ROMP) using Ru‐carbenes (third‐generation Grubbs catalyst) is reported. Phenylene ethynylene trimers are reduced via a Grignard reagent, followed by an intramolecular McMurry cyclization to give the cyclophenes. The cyclophenes are polymerized into soluble poly(para‐phenylene vinylene)s (PPV), which are analyzed in solution by NMR, UV–vis, and fluorescence spectroscopy. They are spin coated into amorphous, fluorescent thin films, and investigated by optical spectroscopy and cyclic voltammetry.
Synthesis and polymerization of two novel 4,7,12,15‐alkoxy‐substituted [2.2.2]‐paracyclophane‐1,9,17‐trienes via ring opening metathesis polymerization is described. The resulting poly(para‐phenylene vinylene)s (PPV) show high solubility and quantum yields and are examined in solution by gel permeation chromatography (GPC), UV–vis, and fluorescence spectroscopy and in solid state by UV–vis, fluorescence spectroscopy, and cyclic voltammetry.