Knoll Christian, Müller Danny, Seifried Marco, Giester Gerald, Welch Jan M, Artner Werner, Hradil Klaudia, Reissner Michael, Weinberger Peter
Institute of Applied Synthetic Chemistry, TU Wien, Getreidemarkt 9/163-AC, 1060 Vienna, Austria.
Dalton Trans. 2018 Apr 24;47(16):5553-5557. doi: 10.1039/c8dt00781k.
Criteria for a technologically relevant spin crossover (SCO) material include temperature and abruptness. A series of Fe(ii) - 1,3-bis((1H-tetrazol-1-yl)methyl)bicyclo[1.1.1]pentane SCO complexes with various anions (BF4-, ClO4-, and PF6-) designed using a structure-property based concept is reported. All complexes feature abrupt SCO-behavior with T1/2 between 170 K and 187 K. These materials demonstrate that without stabilizing the effects of incorporated solvents or a hydrogen bond-network, the observed cooperativity during high-spin-low-spin transition is anion independent and originates only from the rigidity and internal strain of the propellane-moiety in the ligand. Spectroscopy and structural investigations of these materials are supported by quantum chemical calculations.
具有技术相关性的自旋交叉（SCO）材料的标准包括温度和突变性。本文报道了一系列基于结构-性质概念设计的、带有不同阴离子（BF4-、ClO4-和PF6-）的Fe（II）-1,3-双（（1H-四唑-1-基）甲基）双环[1.1.1]戊烷SCO配合物。所有配合物均具有突变的SCO行为，T1/2在170 K至187 K之间。这些材料表明，在没有掺入溶剂或氢键网络的稳定作用的情况下，在高自旋-低自旋转变过程中观察到的协同作用与阴离子无关，仅源于配体中螺旋桨部分的刚性和内部应变。这些材料的光谱和结构研究得到了量子化学计算的支持。
