Romanenko Nikita R, Kuzmin Alexey V, Khasanov Salavat S, Faraonov Maxim A, Yudanova Evgeniya I, Nakano Yoshiaki, Otsuka Akihiro, Yamochi Hideki, Kitagawa Hiroshi, Konarev Dmitri V
Institute of Problems of Chemical Physics RAS, Chernogolovka, Moscow region, 142432 Russia.
Institute of Solid State Physics RAS, Chernogolovka, Moscow region, 142432 Russia.
Dalton Trans. 2022 Feb 8;51(6):2226-2237. doi: 10.1039/d1dt04061h.
Coordination of tin(II) phthalocyanine to transition metal carbonyl clusters in neutral {Sn(Pc)} or radical anion {Sn(Pc˙)} states is reported. Direct interaction of Co(CO) with {Sn(Pc)} yields a crystalline complex {Co(CO)·Sn(Pc)} (1). There is no charge transfer from the cluster to phthalocyanine in 1, which preserves the diamagnetic Pc macrocycle. The Ru(CO) cluster forms complexes with one or two equivalents of {Sn(Pc˙)} to yield crystalline {Cryptand2.2.2}{Ru(CO)·Sn(Pc˙)} (2) or {Cryptand2.2.2}{Ru(CO)·[Sn(Pc˙)]}·4CHCl (3) (M is K or Cs). Paramagnetic {Sn(Pc˙)} species in 2 are packed in -stacking [{Sn(Pc˙)}] dimers, providing strong antiferromagnetic coupling of spins with exchange interaction / = -19 K. Reduction of Ru(CO), Os(CO) and Ir(CO) clusters by decamethylchromocene (CpCr) and subsequent oxidation of the reduced species by {SnCl(Pc)} yield a series of complexes with high-spin CpCr counter cations ( = 3/2): (CpCr){Ru(CO)·Sn(Pc˙)}·CHCl (4), (CpCr){Os(CO)Cl·Sn(Pc˙)}·CHCl (5) and (CpCr){Ir(CO)·Sn(Pc˙)} (6). It is seen that reduced clusters are oxidized by Sn, which is transferred to Sn, whereas the Pc macrocycle is reduced to Pc˙. In the case of Os(CO), oxidation of the metal atom in the cluster is observed to be accompanied by the formation of Os(CO)Cl with one Os center. Rather weak magnetic coupling is observed between paramagnetic CpCr and {Sn(Pc˙)} species in 4, but this exchange interaction is enhanced in 5 owing to Os(CO)Cl clusters with paramagnetic Os ( = 1/2) also being involved in antiferromagnetic coupling of spins. The formation of {Sn(Pc˙)} with radical trianion Pc˙ macrocycles in 2-5 is supported by the appearance of new absorption bands in the NIR spectra and essential N-C bond alternation in Pc (for 3-5). On the whole, this work shows that both diamagnetic {Sn(Pc)} and paramagnetic {Sn(Pc˙)} ligands substitute carbonyl ligands in the transition metal carbonyl clusters, forming well-soluble paramagnetic solids absorbing light in the visible and NIR ranges.
报道了中性{Sn(Pc)}或自由基阴离子{Sn(Pc˙)}状态下锡（II）酞菁与过渡金属羰基簇的配位情况。Co(CO)与{Sn(Pc)}直接相互作用生成晶体配合物{Co(CO)·Sn(Pc)} (1)。在1中不存在从簇到酞菁的电荷转移，这使得抗磁性的酞菁大环得以保留。Ru(CO)簇与一当量或两当量的{Sn(Pc˙)}形成配合物，生成晶体{穴醚2.2.2}{Ru(CO)·Sn(Pc˙)} (2)或{穴醚2.2.2}{Ru(CO)·[Sn(Pc˙)]}·4CHCl (3)（M为K或Cs）。2中的顺磁性{Sn(Pc˙)}物种以 -堆积[{Sn(Pc˙)}]二聚体形式堆积，提供了自旋间强的反铁磁耦合，交换相互作用J = -19 K。用十甲基二茂铬（CpCr）还原Ru(CO)、Os(CO)和Ir(CO)簇，随后用{SnCl(Pc)}氧化还原后的物种，得到一系列具有高自旋CpCr抗衡阳离子（S = 3/2）的配合物：(CpCr){Ru(CO)·Sn(Pc˙)}·CHCl (4)、(CpCr){Os(CO)Cl·Sn(Pc˙)}·CHCl (5)和(CpCr){Ir(CO)·Sn(Pc˙)} (6)。可以看出，还原后的簇被Sn氧化，Sn被转移为Sn，而酞菁大环被还原为Pc˙。在Os(CO)的情况下，观察到簇中金属原子的氧化伴随着一个Os中心的Os(CO)Cl的形成。在4中顺磁性的CpCr和{Sn(Pc˙)}物种之间观察到相当弱的磁耦合，但由于顺磁性Os（S = 1/2）的Os(CO)Cl簇也参与了自旋的反铁磁耦合，这种交换相互作用在5中增强。2 - 5中具有自由基三阴离子Pc˙大环的{Sn(Pc˙)}的形成得到了近红外光谱中新吸收带的出现以及Pc中基本的N - C键交替（对于3 - 5）的支持。总体而言，这项工作表明抗磁性的{Sn(Pc)}和顺磁性的{Sn(Pc˙)}配体都能取代过渡金属羰基簇中的羰基配体，形成在可见光和近红外范围内吸收光的可溶顺磁性固体。
