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High-Spin Polymers: Ferromagnetic Coupling of S = 1 Hexaazacyclophane Units up to a Pure S = 2 Polycyclophane
Lukasz Skorka1, Piotr Kurzep1, Timothée Chauviré2,3
1Faculty of Chemistry, Warsaw University of Technology , Noakowskiego 3, 00-664 Warsaw, Poland.
Abstract:
Triarylamines oxidized to radical cations can be used as stable spins sources for the design of high-spin compounds. Here, we present the synthesis of the polyarylamine-containing hexaazacyclophanes linked via meta-terphenyl bridges. Spins, created after oxidation of the polymer, can be coupled magnetically in cyclophane moieties via meta-phenyl and along the polymer chain via meta-terphenyl units. The formation of a quintet spin state was evidenced by pulsed-EPR nutation spectroscopy. Two exchange coupling constants via both couplers were determined experimentally and corresponded to J/k = 89 K in the cyclophane moiety and j/k = 17 K via meta-terphenyl. Most importantly, in this polymer, four spins can be ferromagnetically ordered via both couplers, which leads to the high spin state.
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