A Host-Guest Electron Transfer Mechanism for Magnetic and Electronic Modifications in a Redox‐Active Metal-Organic Framework
A Host-Guest Electron Transfer Mechanism for Magnetic and Electronic Modifications in a Redox‐Active Metal-Organic Framework
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氧化还原活性金属有机框架中磁性和电子修饰的主客体电子转移机制
DOI：
10.1002/anie.202115976
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发表时间：
2022
期刊：
影响因子：
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通讯作者：
Miyasaka Hitoshi
中科院分区：
文献类型：
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作者：
Zhang Jun;Kosaka Wataru;Kitagawa Yasutaka;Miyasaka Hitoshi
分子框架系统中的主客体电子转移（HGET）是主框架和客体发生剧烈功能变化的关键触发因素。通过层状框架中的 HGET 实现了可逆磁相变，[{Ru2(2,6-F2PhCO2)4}2(BTDA-TCNQ)] (1)，其中 2,6-F2PhCO2− 和 BTDA-TCNQ 代表 2,6-二氟苯甲酸酯， 分别为双[1,2,5]二噻唑四氰基醌二甲烷。通过吸附碘（I2），具有反铁磁基态的无客体1转变为顺磁体[{Ru2(2,6-F2PhCO2)4}2(BTDA-TCNQ)]I3(1-I3)。通过 HGET，[{Ru2II,III}+‐(BTDA‐TCNQ).−‐{Ru2II,II}] in1 的局域电荷分布可逆地修改为 [{Ru2II,III}+‐(BTDA‐TCNQ)0‐{Ru2II,II}](I3−) in1‐I3。 1-I3 的理论计算表明，在弱铁磁耦合的帮助下，部分电荷离域为 [{Ru2}(1−δ)+-(BTDA-TCNQ)0-{Ru2}δ+](I3−)，δ≈0.2。1-I3 的电导率比 1 提高了一百倍。
Host–guest electron transfer (HGET) in molecular framework systems is a critical trigger for drastic functional changes in both host framework and guest. A reversible magnetic phase transition was achieved via HGET in a layered framework, [{Ru2(2,6‐F2PhCO2)4}2(BTDA‐TCNQ)] (1), where 2,6‐F2PhCO2−and BTDA‐TCNQ represent 2,6‐difluorobenzoate and bis[1,2,5]dithiazolotetracyanoquinodimethane, respectively. The guest‐free1with an antiferromagnetic ground state transformed into a paramagnet, [{Ru2(2,6‐F2PhCO2)4}2(BTDA‐TCNQ)]I3(1‐I3), by adsorbing iodine (I2). The local charge distribution of [{Ru2II,III}+‐(BTDA‐TCNQ).−‐{Ru2II,II}] in1was reversibly modified to [{Ru2II,III}+‐(BTDA‐TCNQ)0‐{Ru2II,II}](I3−) in1‐I3through HGET. Theoretical calculations of1‐I3indicated a partial charge delocalization as [{Ru2}(1−δ)+‐(BTDA‐TCNQ)0‐{Ru2}δ+](I3−) withδ≈0.2, aided by weak ferromagnetic coupling.1‐I3exhibited a hundred‐fold enhancement in electrical conductivity compared to that of1.