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Flexibility and Stability of Metal Coordination Macromolecules
Author(s) -
Jiang Heyan,
Geng Diya,
Liu Dapeng,
Lanigan Nicholas,
Wang Xiaosong
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201701133
Subject(s) - macromolecule , isopropyl , structural rigidity , monomer , crystallography , thermal stability , chemistry , metal , rigidity (electromagnetism) , polymerization , flexibility (engineering) , alkyl , stereochemistry , polymer chemistry , materials science , polymer , organic chemistry , biochemistry , geometry , mathematics , statistics , composite material
The effect of chain structure on flexibility and stability of macromolecules containing weak P−Fe metal coordination bonds is studied. Migration insertion polymerization (MIP) of FpC X Fp ( 1 ) and PR 2 C Y PR 2 ( 2 ) (Fp: CpFe(CO) 2 ; C X and C Y : alkyl spacers; P: phosphine; R: phenyl or isopropyl) generates P( 1 / 2 ), in which the P−Fe and Fe−P bonds with opposite bonding direction are alternatively arranged in the backbone. On the other hand, P(FpC X P) synthesized from AB‐type monomers (FpC X P) has P−Fe bonds arranged in the same direction. P( 1 / 2 ) is more rigid and stable than P(FpC X P), which is attributed to the chain conformation resulting from the P−Fe bonding direction. In addition, the longer spacers render P( 1 / 2 ) relatively flexible; the phenyl substituents, as compared with the isopropyl groups, improves the rigidity, thermal, and solution stability of P( 1 / 2 ). It is therefore possible to incorporate weak metal coordination bonds into macromolecules with improved stability and adjustable flexibility for material processing.