Abrupt spin transition in a modified-terpyridine cobalt(ii) complex with a highly-distorted [CoN6] core
Abrupt spin transition in a modified-terpyridine cobalt(ii) complex with a highly-distorted [CoN6] core
复制标题
具有高度扭曲的 [CoN6] 核的改性三联吡啶钴 (ii) 络合物中的突变自旋跃迁
DOI：
10.1039/c8dt02367k
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发表时间：
2018
影响因子：
4
通讯作者：
Hayami Shinya
中科院分区：
文献类型：
--
作者：
Nakaya Manabu;Ohtani Ryo;Shin Jong Won;Nakamura Masaaki;Lindoy Leonard F.;Hayami Shinya
[Co(naph-C2-terpy)2](BF4)2(1；naph-C2-terpy=4′-(2-naphthoxy(ethoxy))-2，2′：6′，2′′-terpyridine)，)钴(II)络合物的π共轭取代基[Co(naph-C2-terpy)2](BF4)2(1；naph-C2-terpy=Naph)表现出突然的自旋转变(ST)行为(合作因子C=0.91)，而其溶剂化产物1·2MeOH则表现出逐渐的自旋交叉(SCO)行为(C=0.49)。X-射线单晶结构分析表明，1中的八面体配位核[CoN6]在高自旋态和低自旋态都比溶剂化的1·2MeOH或其他两个衍生物[Co(R-terpy)2](BF4)2(R=2-萘基(2)，9-菲(3))具有更大的畸变率。将各自的变形参数(Σ)与以前报道的SCO钴(II)化合物的变形参数(DEA)进行了比较。分子间强相互作用稳定了高度扭曲的[CoN_6]核(HS态和LS态的Σ分别为126和101.6)，并观察到突变的ST行为。
The cobalt(II) complex incorporating π-conjugated substituent, [Co(Naph-C2-terpy)2](BF4)2 (1; Naph-C2-terpy = 4′-(2-naphthoxy(ethoxy))-2,2′:6′,2′′-terpyridine), exhibits an abrupt spin transition (ST) behavior (cooperative factor C = 0.91) while its solvated product, 1·2MeOH, shows gradual spin crossover (SCO) behavior (C = 0.49). Single crystal X-ray structural analyses demonstrated that the octahedral coordination core [CoN6] in 1 shows larger distortion in both high-spin and low-spin states than solvated 1·2MeOH or another two derivatives, [Co(R-terpy)2](BF4)2 (R = 2-naphthyl (2), 9-anthracenyl (3)). The respective distortion parameters (Σ) are compared with those for previously reported SCO cobalt(II) compounds. The highly-distorted [CoN6] core in 1 (Σ = 126 in the HS state and 101.6 in the LS state) was stabilized by strong intermolecular interactions and observed an abrupt ST behaviour.