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Polyacetylenes with Ferrocenophane Pendant Groups: Synthesis by Rh‐Complex‐Catalyzed Polyaddition, Characterization and Properties
Author(s) -
Sakano Tatsuaki,
Osakada Kohtaro
Publication year - 2001
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/1521-3935(20010601)202:9<1829::aid-macp1829>3.0.co;2-p
Subject(s) - monomer , polymer chemistry , copolymer , chemistry , polymerization , polymer , tetrahydrofuran , thermal decomposition , ring opening polymerization , organic chemistry , solvent
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 CHCl 3 , 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 M̄ n = 10 000 and M̄ w = 14 000, and M̄ n = 5 100 and M̄ w = 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 M̄ n = 8 800 and M̄ w = 13 200 to M̄ n = 23 800 and M̄ w = 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.