Faraonov Maxim A, Yudanova Evgeniya I, Kuzmin Alexey V, Yakushev Ilya A, Khasanov Salavat S, Otsuka Akihiro, Yamochi Hideki, Kitagawa Hiroshi, Konarev Dmitri V
Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry RAS, Chernogolovka, Moscow Region, 142432, Russia.
Institute of Solid State Physics RAS, Chernogolovka, Moscow Region, 142432 Russia.
Dalton Trans. 2023 Aug 29;52(34):12049-12056. doi: 10.1039/d3dt01498c.
Heterobimetallic {[Co(CO)][In(Pc)]} (1) and (CpCr){[Mn(CO)][In(Pc˙)]}·2CHCl (2) complexes based on indium(III) phthalocyanine (Pc) were obtained as crystals. The complexes were synthesized by single (1) and double (2) reduction of indium(III) phthalocyanine chloride in the presence of transition metal carbonyls. Complex 1 contains dianionic Pc macrocycles. Thus, the coordinated Co(CO) carbonyl accepts an electron in the one-electron reduction forming a diamagnetic [Co(CO)] anion. Complex 2 contains a heterobimetallic {[Mn(CO)][In(Pc˙)]} anion and paramagnetic CpCr counter cations. Therefore, in the double reduction, electrons are transferred to Mn(CO) forming a diamagnetic [Mn(CO)] anion and to the Pc macrocycle forming a paramagnetic radical Pc˙ trianion. Such assignments for 1 and 2 are in line with optical spectra, crystal structures and the data of magnetic measurements. The spectrum of 1 in the UV-visible range is similar to that of the starting InClPc. The formation of 2 is accompanied by an essential blue-shift of the Q-band of Pc as well as by the appearance of an intense NIR band at 1005 nm characteristic of Pc˙. Compound 1 is EPR silent and diamagnetic, whereas the value of the effective magnetic moment of 2 is 4.24 at 300 K, which corresponds to the contribution of = 1/2 (Pc˙) and = 3/2 (Cp*Cr) spins. Both weakly coupled paramagnetic centers ( = -0.41 cm) are observed in the EPR spectra.
基于铟（III）酞菁（Pc）的异双金属配合物{[Co(CO)][In(Pc)]}（1）和（CpCr）{[Mn(CO)][In(Pc˙)]}·2CHCl（2）以晶体形式获得。这些配合物是在过渡金属羰基化合物存在下，通过对氯化铟（III）酞菁进行单还原（1）和双还原（2）合成的。配合物1包含二价阴离子型Pc大环。因此，配位的Co(CO)羰基在单电子还原过程中接受一个电子，形成抗磁性的[Co(CO)]阴离子。配合物2包含一个异双金属{[Mn(CO)][In(Pc˙)]}阴离子和顺磁性的CpCr抗衡阳离子。所以，在双还原过程中，电子转移到Mn(CO)形成抗磁性的[Mn(CO)]阴离子，并转移到Pc大环形成顺磁性的自由基Pc˙三价阴离子。对1和2的这种归属与光谱、晶体结构以及磁性测量数据相符。1在紫外-可见范围内的光谱与起始的InClPc相似。2的形成伴随着Pc的Q带显著蓝移以及在1005 nm处出现一个强烈的近红外带，这是Pc˙的特征。化合物1是EPR沉默且抗磁性的，而2在300 K时的有效磁矩值为4.24，这对应于S = 1/2（Pc˙）和S = 3/2（Cp*Cr）自旋的贡献。在EPR光谱中观察到了两个弱耦合的顺磁性中心（J = -0.41 cm）。
