Heterotrimetallic paramagnetic complex of ring reduced tin(II) hexadecachlorophthalocyanine
Heterotrimetallic paramagnetic complex of ring reduced tin(II) hexadecachlorophthalocyanine
复制标题
环还原十六氯酞菁锡(II)的异三金属顺磁络合物
DOI：
10.1039/d3nj00506b
复制
发表时间：
2023
影响因子：
3.3
通讯作者：
Konarev Dmitri V.
中科院分区：
文献类型：
--
作者：
Romanenko Nikita R.;Faraonov Maxim A.;Osipov Nikita G.;Kuzmin Alexey V.;Khasanov Salavat S.;Otsuka Akihiro;Yamochi Hideki;Kitagawa Hiroshi;Konarev Dmitri V.
在{CpFeI(CO)2}2的存在下，用十甲基二茂铬（Cp*2Cr）还原锡（IV）二氯化十六氯眼青碱（PcCl16），得到了配位配合物(Cp*2CrIII)+{CpFeII(CO)2(SnII[PcCl16]4−)}−(1)。该过程伴随着CrII和FeI中心的氧化，形成顺磁性的CrIII和反磁性的FeII。发生了大环的双电子还原和抗磁性[PcCl16]4−的形成以及锡（IV）向锡（II）的转变。[PcCl16]4−四阴离子形成于（隐式（K+））2{SnIVCl2[PcCl16]4−}2−·2C6H4Cl2(2)中，由温和还原剂-富勒烯C60˙−自由基阴离子还原SnIVPcCl16得到。配合物1和2以晶体形式析出。三明治式组件在1中形成。两个(Cp*2CrIII)+阳离子夹在两个{CpFeII(CO)2(SnII[PcCl16]4−)}−平面之间，而{SnIVCl2[PcCl16]4−}2−大环层则在2中形成。结构分析、光谱学和磁测量数据支持了1和2中[PcCl16]4−四阴离子的形成。磁化率测量对应于每个公式单位一个非相互作用的CrIII自旋（S = 3/2）的贡献。在自旋之间观察到弱反铁磁耦合。只有CrIII原子对1的EPR谱有贡献，而盐2是抗磁性的，并且EPR无反应。
Coordination complex (Cp*2CrIII)+{CpFeII(CO)2(SnII[PcCl16]4−)}− (1) has been obtained by the reduction of tin(IV) dichloride hexadecachlorophthalocyanine (PcCl16) by decamethylchromocene (Cp*2Cr) in the presence of {CpFeI(CO)2}2. The process is accompanied by oxidation of CrII and FeI centers and the formation of paramagnetic CrIII and diamagnetic FeII species. Two-electron reduction of a macrocycle and the formation of diamagnetic [PcCl16]4− as well as a transition of tin(IV) to tin(II) occur. The [PcCl16]4− tetraanions are formed in (cryptand(K+))2{SnIVCl2[PcCl16]4−}2−·2C6H4Cl2 (2) obtained by the reduction of SnIVPcCl16 by mild reductant – fullerene C60˙− radical anions. Complexes 1 and 2 precipitate as crystals. Sandwich-type assemblies are formed in 1. Two (Cp*2CrIII)+ cations are sandwiched between two {CpFeII(CO)2(SnII[PcCl16]4−)}− planes, whereas layers of the {SnIVCl2[PcCl16]4−}2− macrocycles are formed in 2. The formation of the [PcCl16]4− tetraanions in both 1 and 2 is supported by the data of structural analysis, optical spectroscopy and magnetic measurements. Susceptibility measurements correspond to the contribution of one non-interacting CrIII spin (S = 3/2) per formula unit. Weak antiferromagnetic coupling is observed between the spins. Only CrIII atoms contribute to EPR spectra of 1, whereas salt 2 is diamagnetic and EPR silent.