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二氯酞菁锡（IV）与十甲基金属茂（M = Cr和Co）的反应。（Cp*Co）{SnCl（Pc˙）}˙·2CHCl中自旋的强磁耦合。

Reaction of tin(iv) phthalocyanine dichloride with decamethylmetallocenes (M = Cr and Co). Strong magnetic coupling of spins in (Cp*Co){SnCl(Pc˙)}˙·2CHCl.

作者信息

Konarev Dmitri V, Troyanov Sergey I, Shestakov Alexander F, Yudanova Evgeniya I, Otsuka Akihiro, Yamochi Hideki, Kitagawa Hiroshi, Lyubovskaya Rimma N

机构信息

Institute of Problems of Chemical Physics RAS, Chernogolovka, Moscow Region, 142432 Russia.

出版信息

Dalton Trans. 2018 Jan 23;47(4):1243-1250. doi: 10.1039/c7dt03807k.

DOI:10.1039/c7dt03807k
PMID:29299581
Abstract

The reaction of tin(iv) phthalocyanine dichloride {SnCl(Pc)} with decamethylmetallocenes (CpM, M = Co, Cr) has been studied. Decamethylcobaltocene reduces SnCl(Pc) to form the (CpCo){SnCl(Pc˙)}˙·2CHCl (1) complex. The negative charge of {SnCl(Pc˙)}˙ 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 1.68μ at 300 K, indicating the contribution of one S = 1/2 spin of the Pc˙ 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 SnCl(Pc) to form the [(CpCr){SnCl(Pc˙)}˙ complex but further reaction between the ions is observed. This reaction is accompanied by the substitution of one Cp ligand of CpCr by chloride anions originating from {SnCl(Pc˙)}˙ to form the complex {(CpCrCl)(Sn(μ-Cl)(Pc))}·CHCl (2) in which the (CpCrCl) and {Sn(Pc)} species are bonded through the μ-bridged Cl anion. According to the DFT calculations, this reaction proceeds via an intermediate [(CpCrCl)(SnClPc)] complex.

摘要

已对二氯酞菁锡（IV）{SnCl(Pc)}与十甲基茂金属（CpM，M = Co，Cr）的反应进行了研究。十甲基钴ocene将SnCl(Pc)还原以形成（CpCo）{SnCl(Pc˙)}˙·2CHCl（1）配合物。{SnCl(Pc˙)}˙的负电荷在Pc大环上离域，导致C-N（亚胺）键交替，在近红外范围内出现新带，并且在1的光谱中Soret带和Q带都发生强烈蓝移。1在300 K时的磁矩等于1.68μ，表明Pc˙大环的一个S = 1/2自旋有贡献。这些大环在1中形成紧密堆积的双堆叠，具有有效的π-π相互作用，在-80 K的魏斯温度下提供自旋的强反铁磁耦合。十甲基铬ocene最初也将SnCl(Pc)还原以形成[(CpCr){SnCl(Pc˙)}˙配合物，但观察到离子之间进一步反应。该反应伴随着CpCr的一个Cp配体被源自{SnCl(Pc˙)}˙的氯离子取代，形成配合物{(CpCrCl)(Sn(μ-Cl)(Pc))}·CHCl（2），其中（CpCrCl）和{Sn(Pc)}物种通过μ桥连的Cl阴离子键合。根据DFT计算，该反应通过中间体[(CpCrCl)(SnClPc)]配合物进行。

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