Skorka Lukasz, Kurzep Piotr, Chauviré Timothée, Dubois Lionel, Mouesca Jean-Marie, Maurel Vincent, Kulszewicz-Bajer Irena
Faculty of Chemistry, Warsaw University of Technology , Noakowskiego 3, 00-664 Warsaw, Poland.
Université Grenoble Alpes, INAC, SyMMES , F-38000 Grenoble, France.
J Phys Chem B. 2017 Apr 27;121(16):4293-4298. doi: 10.1021/acs.jpcb.7b01531. Epub 2017 Apr 7.
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.
氧化成自由基阳离子的三芳基胺可作为稳定的自旋源用于高自旋化合物的设计。在此，我们展示了通过间三联苯桥连接的含聚芳胺六氮杂环蕃的合成。聚合物氧化后产生的自旋可通过间位苯基在环蕃部分进行磁耦合，并通过间三联苯单元沿聚合物链进行磁耦合。脉冲电子顺磁共振章动光谱证实了五重态自旋态的形成。通过两种耦合剂的两个交换耦合常数通过实验测定，在环蕃部分对应于J/k = 89 K，通过间三联苯的j/k = 17 K。最重要的是，在这种聚合物中，四个自旋可通过两种耦合剂进行铁磁有序排列，这导致了高自旋态。
