Reaction of tin(iv) phthalocyanine dichloride with decamethylmetallocenes (M = CrII and CoII). Strong magnetic coupling of spins in (Cp*2Co+){SnIVCl2(Pc・3-)}・-・2C6H4Cl2
Reaction of tin(iv) phthalocyanine dichloride with decamethylmetallocenes (M = CrII and CoII). Strong magnetic coupling of spins in (Cp*2Co+){SnIVCl2(Pc・3-)}・-・2C6H4Cl2
复制标题
二氯化锡(iv)酞菁与十甲基茂金属（M = CrII 和 CoII）的反应（Cp*2Co+）{SnIVCl2(Pc・3-)}・-・2C6H4Cl2 中的自旋强磁耦合。
DOI：
10.1039/c7dt03807k
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发表时间：
2018
影响因子：
4
通讯作者：
Lyubovskaya Rimma N.
中科院分区：
文献类型：
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作者：
Konarev Dmitri V.;Troyanov Sergey I.;Shestakov Alexander F.;Yudanova Evgeniya I.;Otsuka Akihiro;Yamochi Hideki;Kitagawa Hiroshi;Lyubovskaya Rimma N.
研究了二氯化亚锡(SnIVCl2(PC2−))与十甲基茂金属(Cp*2M，M=Co，Cr)的反应。十甲基钴还原SnIVCl2(PC2−)形成(Cp*2Co+){SnIVCl2(Pc·3−)}·−·2C6H4Cl2(1)配合物。{SnIVCl2(Pc·3−)}·−的负电荷在Pc大循环中离域，提供了C-N(亚胺)键的交替，在近红外光谱中出现了新的带，并且在1的光谱中SORET和Q带都发生了强烈的蓝移。在300K下，1的磁矩等于1.68μB，表明Pc·3−大循环中一个S=1/2自旋的贡献。这些大环与有效的π-π相互作用形成紧密堆积在1中的双堆栈，在−80K的魏斯温度下提供了强烈的自旋反铁磁性耦合。十甲基铬最初也还原SnIVCl2(Pc2−)形成[(Cp*2Cr+){SnVICl2(Pc·3−)}·−络合物，但观察到离子之间的进一步反应。反应还伴随着Cp*2Cr的一个Cp*配体被来自{SnIVCl2(Pc·3−)}·−的氯离子取代，形成了配合物{(Cp*CrCl2)(SnIV(μ-Cl)(Pc2−))}·C6H4Cl2(2)，其中(Cp*CrCl2)和{SnIV(Pc2−)}通过μ桥联的Cl−阴离子键合。根据密度泛函理论计算，该反应是通过中间体[(Cp*2CrCl)(SnClPc)]络合物进行的。
The reaction of tin(IV) phthalocyanine dichloride {SnIVCl2(Pc2−)} with decamethylmetallocenes (Cp*2M, M = Co, Cr) has been studied. Decamethylcobaltocene reduces SnIVCl2(Pc2−) to form the (Cp*2Co+){SnIVCl2(Pc˙3−)}˙−·2C6H4Cl2 (1) complex. The negative charge of {SnIVCl2(Pc˙3−)}˙− is delocalized over the Pc macrocycle providing the alternation of the C–N(imine) bonds, the appearance of new bands in the NIR range and a strong blue shift of both the Soret and Q-bands in the spectrum of 1. The magnetic moment of 1 is equal to 1.68μB at 300 K, indicating the contribution of one S = 1/2 spin of the Pc˙3− macrocycles. These macrocycles form closely packed double stacks in 1 with effective π–π interactions providing strong antiferromagnetic coupling of spins at a Weiss temperature of −80 K. Decamethylchromocene initially also reduces SnIVCl2(Pc2−) to form the [(Cp*2Cr+){SnVICl2(Pc˙3−)}˙− complex but further reaction between the ions is observed. This reaction is accompanied by the substitution of one Cp* ligand of Cp*2Cr by chloride anions originating from {SnIVCl2(Pc˙3−)}˙− to form the complex {(Cp*CrCl2)(SnIV(μ-Cl)(Pc2−))}·C6H4Cl2 (2) in which the (Cp*CrCl2) and {SnIV(Pc2−)} species are bonded through the μ-bridged Cl− anion. According to the DFT calculations, this reaction proceeds via an intermediate [(Cp*2CrCl)(SnClPc)] complex.