Preparation of Head‐to‐Tail Regioregular 6‐(1‐Alkenyl)‐Functionalized Poly(pyridine‐2, 5‐diyl) and its Post‐Functionalization via Hydroboration. Issue 23 (6th November 2015)

• Record Type: Journal Article
• Authors: Grandl, Markus; Pammer, Frank
• Is Part Of: Macromolecular chemistry and physics. Volume 216:Issue 23(2015:Dec.)
• Page Start: 2249
• Page End: 2262
• Publication Date: 2015-11-06
• Subjects: conjugated polymers polypyridines -- hydroboration -- Kumada‐coupling -- post‐functionalization; Polymers -- Periodicals; Polymerization -- Periodicals; Synthetic products -- Periodicals; Macromolecules -- Periodicals; 547.7
• DOI: 10.1002/macp.201500337
• Languages: English
• ISSNs: 1022-1352

Abstract

Abstract : In this work, the preparation of head‐to‐tail regioregular poly(6‐(1‐tridecenyl)‐pyridine‐2, 5‐diyl) (PPy ) and its post‐functionalization via hydroboration is described.PPy has been prepared via Kumada‐coupling polycondensation with different catalytic systems. Number‐average molecular weights of up to M n = 14.7 kDa (PDI = 2.0, DPn = 60) can be obtained, as determined by gel permeation chromatography relative to polystyrene standards.PPy has been characterized by MALDI‐TOF MS, optical spectroscopy, and cyclic voltammetry. The regioregularity of the material is confirmed by comparison with a head‐to‐head‐tail‐to‐tail regioregular polybipyridine (PBPy, M n = 14.0 kDa, PDI = 1.5, DPn = 29). The 1‐alkenyl‐substituents inPPy have been introduced to provide functional groups for post‐functionalization. Herein, it is also demonstrated that these internal double‐bonds are sufficiently reactive to allow for hydroboration with 9 H ‐borabicyclo[3.3.1]nonane (9 H ‐BBN), to furnish an intermediate borylated polymer (PPyHB ). Treatment ofPPyHB with strong acids, and characterization of the deborylated polymerPPyH2 proves quantitative conversion of the precursor polymer. Abstract : Post‐functionalization of 6‐alkenyl poly­pyridine‐2, 5‐diyls . A new head‐to‐tail regioregular (1‐alkenyl)‐substituted poly­pyridine has been prepared, and its regioregularity has been confirmed via comparison with head‐to‐head‐tail‐to‐tail regioregular polybipyridine. Herein it is demonstrated that the 1‐alkenyl‐substitutents allow for quantitative post‐functionalization via hydroboration, and thereby allow for the modification of electronic and physical properties.