Solvent‐Dependent Spin‐Crossover Behavior in Semiconducting Co–Crystals of [Fe(1‐bpp) 2 ] 2+ Cations and TCNQ δ− Anions (0
Solvent‐Dependent Spin‐Crossover Behavior in Semiconducting Co–Crystals of [Fe(1‐bpp) 2 ] 2+ Cations and TCNQ δ− Anions (0
复制标题
溶剂 — 相关自旋 — [Fe(1 — bpp) 2 ] 2 阳离子和 TCNQ 阴离子 (0
DOI：
10.1002/ejic.202100707
复制
发表时间：
2021
影响因子：
2.3
通讯作者：
Shatruk, Michael
中科院分区：
文献类型：
--
作者：
Üngör, Ökten;Choi, Eun Sang;Shatruk, Michael
自旋交叉（SCO）阳离子配合物[Fe(1‐bpp)2]2+（1‐bpp=2,6‐双（吡唑‐1‐基）吡啶）与分数电荷有机阴离子TCNQδ−(0<δ<1)共结晶，得到杂化材料[Fe(1‐bpp)2](TCNQ)3.5⋅3.5MeCN(1)和[Fe(1‐bpp)2](TCNQ)4⋅4DCE(2)，其中TCNQ=7,7,8,8‐四氰喹二甲烷，MeCN=乙腈，DCE=1,2‐二氯乙烷。两种材料均表现出半导体特性，室温电导率分别为1.1×10−4S/cm和1.7×10−3S/cm。这两种配合物的磁性行为与间隙溶剂的含量密切相关。络合物1经历了一个逐渐的温度驱动的SCO过程，中点温度为t1 /2=234 K。部分溶剂损失导致t1 /2值升高，而完全脱溶使材料在整个研究温度范围内具有高自旋（HS）。在2的情况下，溶剂化配合物仅在被母液覆盖时才表现出t1 /2=166 K的逐渐SCO，而即使在室温下，间隙溶剂也容易损失，导致HS - only行为。
Co‐crystallization of the spin‐crossover (SCO) cationic complex, [Fe(1‐bpp)2]2+(1‐bpp=2,6‐bis(pyrazol‐1‐yl)pyridine) with fractionally charged organic anion TCNQδ−(0<δ<1) afforded hybrid materials [Fe(1‐bpp)2](TCNQ)3.5⋅ 3.5MeCN (1) and [Fe(1‐bpp)2](TCNQ)4⋅ 4DCE (2), where TCNQ=7,7,8,8‐tetracyanoquinodimethane, MeCN=acetonitrile, and DCE=1,2‐dichloroethane. Both materials exhibit semiconducting behavior, with the room‐temperature conductivity values of 1.1×10−4S/cm and 1.7×10−3S/cm, respectively. The magnetic behavior of both complexes exhibits strong dependence on the content of the interstitial solvent. Complex1undergoes a gradual temperature‐driven SCO, with the midpoint temperature ofT1/2=234 K. The partial solvent loss by1leads to the increase in theT1/2value while complete desolvation renders the material high‐spin (HS) in the entire studied temperature range. In the case of2, the solvated complex shows a gradual SCO withT1/2=166 K only when covered with a mother liquid, while the facile loss of interstitial solvent, even at room temperature, leads to the HS‐only behavior.