Hyperbranched poly(ferrocenylphenylenes) (hb-PFPs) with high molecular weights were synthesized
by the copolycyclotrimerizations of (E,E)-1,1‘-bis[2-(4-ethynylphenyl)vinyl]ferrocene (1) with (E)-1-[2-(4-ethynylphenyl)vinyl]ferrocene (2) catalyzed by TaCl5−Ph4Sn at room temperature in high yields (up to 97%).
Effects of reaction conditions, such as monomer and catalyst concentrations, reaction time and molar feed ratio
(r
1
/
2
), on the copolycyclotrimerization were investigated. Solubility of the copolymer is decreased with an increase
in its content of diyne component (N
1
/N
2
). The hb-PFPs were characterized by IR, NMR, UV, CV and TGA
analyses. The copolymers are redox active, whose oxidation potentials are decreased with an increase in N
1
/N
2
.
They are thermally stable, losing ∼5% of weights when heated to 384−400 °C and retaining ∼70% of weights
when pyrolyzed at 1200 °C. The complexation with cobalt carbonyl further metallizes the hb-PFPs and the pyrolytic
ceramization of the cobalt−polymer complexes yields soft ferromagnetic ceramics with high magnetizability (M
s
up to ∼126 emu/g) and low coercivity (H
c down to ∼0.068 kOe).
Three chiral 3D metal–carboxylate frameworks have been successfully synthesized, featuring four-fold helical metal chains as SBUs. Co-MOFs could recognize enantio-selectively α-hydroxy/amino acids by the change of CD signals.
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