Polymers and polymer-metal complexes containing pendent 2,2':6',2"-terpyridinyl ligands

Abstract

Homopolymers and styrene copolymen derived from 4'-viny1-2,2':6',2''-terpyridinyl were prepared in chlorobenzene a t 60 OC by using azobis(isobutyronitri1e) (AIBN) initiation, and monomer reactivity ratios were determined for the styrene copolymers. These polymeric systems containing pendent terpyridinyl ligands readily formed complexes with Co, Cu, and Zn cations. Although vinylterpyridinyl cobalt and ruthenium complex monomers did not undergo homopolymerization with AIBN initiation, they readily formed styrene copolymers under these polymerization conditions. Removal of the metal ions from these polymer-metal complexes occurred readily on washing the complex with acid.ABSTRACT Polymerization of dipropargylsilanes [RR'Si(CH2C4H)2; R, R' = CH3 or Ph] was examined for various transition-metal catalyst systems. A molybdenum complex was found to be a particularly effective catalyst for the cyclopolymerization of dipropargylsilanes. Polymerization of methylphenyldipropargylsilane and diphenyldipropargylsiie by various catalysts leads to soluble, highly colored polymers of average molecular weight 7000-15 000. Polymerization of dimethyldipropargylsilane under the same conditions, however, gives only a partially soluble polymer. IR, 'H NMR, and UV-visible spectroscopies showed that poly(methy1phenyldipropargylsilane) and poly(diphenyldipropargylsi1ane) possess polyene structures having cyclic recurring units in the polymer backbone. Poly(dipropargylsilane)s have been investigated in terms of physical properties, the nature of the doping process, electrical conductivity, and thermal and oxidative stability. The size of substituents was important for the cyclopolymerization tendency and for the resulting polymer properties.

Metal–Ligand‐Containing Polymers: Terpyridine as the Supramolecular Unit

“…It appears that the initial reports on macromolecules containing metal complexes, or at least terpy, can be traced back over more than 20 years ago with the initial reports by Potts and Usifer [34] and Hanabusa et al, [27,28] in which they reported the conventional radical (co)polymerization of vinyl functionalized terpys. The initial polymers [34] had molecular weight distributions (MWD) of 10 to 44 depending on the position of the vinyl bond.…”

“…The initial polymers [34] had molecular weight distributions (MWD) of 10 to 44 depending on the position of the vinyl bond. Copolymers with styrene had narrower MWDs but were still significantly broad; the reactivity ratios between styrene and 4 0 -viny1-2,2 0 :6 0 ,2 00 -terpyridinyl were determined to be 0.47 and 1.12, respectively.…”

Polymers that Contain Ligated Metals in their Side Chain: Building a Foundation for Functional Materials in Opto‐Electronic Applications with an Emphasis on Lanthanide Ions

“…[2,6] Similarly, the influence of self-assembly has driven many examples containing ligated metals at the chain terminus or in the polymer side-chain. [7][8][9][10][11][12][13][14][15][16][17][18][19] The first reports of polymers with terpyridine units in the sidechain showed that 4 0 -vinyl-2,2 0 :6 0 ,2 00 -terpyridinyl readily formed homopolymers as well as styrenic copolymers using traditional free radical methods. [16,17] Similar polymers and their transition metal complexes were investigated a few years later.…”

“…[16,17] Similar polymers and their transition metal complexes were investigated a few years later. [18,19] The preparation of polymeric systems that contain terpyridine (terpy) in the side-chain has been limited, in general, because of the lack of room temperature emission properties from transition metal complexes; [20,21] however, terpy binds to a range of lanthanide ions resulting in excellent luminescence. [4,[22][23][24] This Feature Article will attempt to highlight some of the recent progress in the area of side-chain metalcontaining polymers with a direct focus on electro-optic, namely emissive properties.…”

Design of supramolecular metal complexing polymers: synthesis, complexation, and polymerization of 5,5"-bisfunctionalized terpyridine building blocks

“…However, only a few examples have been published that use these interesting units as building blocks for new block copolymers (see e.g. [10][11][12]) which could provide very interesting functional materials. We describe here a new approach for the synthesis of 5,5"-bisfunctionalized terpyridine ligands as building blocks for the preparation of threeblock and multiblock copolymers.…”