Polyacetylenes with Ferrocenophane Pendant Groups: Synthesis by Rh-Complex-Catalyzed Polyaddition, Characterization and Properties

Abstract

The Rh(I)‐complex‐catalyzed polymerization of N‐(4‐propynyloxyphenyl)‐2‐aza‐[3]‐ferrocenophane (1) and of N‐(4‐pentynyloxyphenyl)‐2‐aza‐[3]‐ferrocenophane (2) gives the corresponding polyacetylenes with ferrocenophane pendant groups; compounds 3 and 4, respectively. Polymers 3 and 4 are soluble in organic solvents such as tetrahydrofuran and CHCl3 , although polymer 3 contains a small portion of an insoluble fraction. The molecular weights of polymers 3 (soluble part) and 4 are determined to be M̄n = 10 000 and M̄w = 14 000, and M̄n = 5 100 and M̄w = 9 300, respectively. The copolymerization of 1 and 4‐ethynyltoluene yields copolymers containing the two monomer units in various ratios depending on the ratio of the monomers used in the polymerization. Molecular weights of the copolymers range from M̄n = 8 800 and M̄w = 13 200 to M̄n = 23 800 and M̄w = 36 900, and increase with a decreasing content of monomer units derived from 1. The thermal decomposition temperature is also influenced linearly over a wide range by the monomer unit ratios. All these polymers are characterized by NMR and UV spectroscopies as well as by elemental analyses. The polymers undergo two electrochemical oxidations: quasi‐reversible oxidation of the Fe and irreversible oxidation of the nitrogen‐containing part of the ferrocenophane unit.

Oligomerization of phenylferrocenylacetylene under the action of WCl6

“…Only decades later [8], the Schrock metathesis catalyst, Mo(N-2,6-Me 2 C 6 H 3 )(CHCMe 2 Ph) [OCMe(CF 3 ) 2 ] 2 , has been employed in ethynylferrocene polymerization to furnish well soluble polyene polymers with up 50 double bonds. Polymerization of N-(4-propynyloxy)-2-aza- [3]-ferrocenophane, catalyzed by the Rh(I) complex, produced polyenes with pendant ferrocenophane [9]. The polymerization of diphenylacetylenes containing the ferrocenyl group in para-or meta-positions was accomplished in the presence of catalytic system TaCl 5 -nBu 4 Sn [10].…”

Synthesis and luminescence of poly(phenylacetylene)s with pendant iridium complexes and carbazole groups

“…Surprisingly, very few polyacetylenes with pendant metal complexes have been described. Among them, the most studied are poly(ethynylferrocene) or poly(ethynylrutenocene) 19–28. Other metallopolyacetylenes reported are poly(phenylacetylene)s bearing Zn phorphirine29 or Ru tris(imine)30 complexes.…”