Konarev Dmitri V, Kuzmin Alexey V, Batov Mikhail S, Khasanov Salavat S, Otsuka Akihiro, Yamochi Hideki, Kitagawa Hiroshi, Lyubovskaya Rimma N
Institute of Problems of Chemical Physics RAS, Chernogolovka, Moscow Region 142432, Russia.
Institute of Solid State Physics RAS, Chernogolovka, Moscow Region 142432, Russia.
ACS Omega. 2018 Nov 5;3(11):14875-14888. doi: 10.1021/acsomega.8b02221. eCollection 2018 Nov 30.
Neutral {CpFe(CO)[Sn(Pc)]} {Cp is cyclopentadienyl (, ) or Cp* is pentamethylcyclopentadienyl (); Pc: phthalocyanine}, {CpFe(CO)[Sn(Nc)]} (, Nc: naphthalocyanine), and {CpFe(CO)[Sn(TPP)]} (, TPP: tetraphenylporphyrin) complexes in which CpFe(CO) fragments (Cp: Cp or Cp) are coordinated to Sn(macrocycle) have been obtained. The product complexes were obtained at the reaction of charge transfer from CpFe(CO) (Cp: Cp or Cp*) to [Sn(macrocycle)] to form the diamagnetic Fe and paramagnetic radical trianionic macrocycles. As a result, these formally neutral complexes contain = 1/2 spins delocalized over the macrocycles. This provides alternation of the C-N or C-C bonds in the macrocycles, the appearance of new bands in the near-infrared spectra of the complexes, and blue shift of both Soret and Q-bands. The {CpFe(CO)Sn(macrocycle)} units (Cp: Cp or Cp*, macrocycle: Pc or Nc) form closely packed π-stacking dimers in and or one-dimensional chains in and with effective π-π interaction between the macrocycles. Such packing allows strong antiferromagnetic coupling between = 1/2 spins. Magnetic interaction can be described well by the Heisenberg model for the isolated dimers in and with exchange interaction / = -78 and -85 K, respectively. Magnetic behavior of and is described well by the model that includes contributions from an antiferromagnetically coupled = 1/2 dimer ( ) and a Heisenberg = 1/2 chain with alternating antiferromagnetic spin exchange between the neighbors ( ). Compound demonstrates large intradimer interaction of / = -54 K and essentially weaker interdimer exchange interactions of / = -6 K, whereas compound shows strong magnetic coupling of spins within the dimers ( / = -170 K) as well as between the dimers ( / = -40 K). Compound {CpFe(CO)[Sn(TPP)]} () shows no π-π interactions between the porphyrin macrocycles, and magnetic coupling is weak in this case (Weiss temperature is -5 K). Preparation of a similar complex with indium(III) chloride phthalocyanine yields {CpFe(CO)[In(Pc)]} (). In this complex, indium(III) atoms are reduced instead of the phthalocyanine macrocycles that explains electron paramagnetic resonance silence of in the 4-295 K range.
已获得中性配合物{CpFe(CO)[Sn(Pc)]}（其中Cp为环戊二烯基（，）或Cp为五甲基环戊二烯基（）；Pc：酞菁）、{CpFe(CO)[Sn(Nc)]}（，Nc：萘酞菁）和{CpFe(CO)[Sn(TPP)]}（，TPP：四苯基卟啉），其中CpFe(CO)片段（Cp：Cp或Cp*）与Sn（大环）配位。产物配合物是通过从CpFe(CO)（Cp：Cp或Cp*）到[Sn（大环）]的电荷转移反应形成抗磁性的Fe和顺磁性的自由基三阴离子大环而得到的。结果，这些形式上中性的配合物含有1/2自旋，其在大环上离域。这导致大环中C-N或C-C键的交替、配合物近红外光谱中出现新的谱带以及Soret带和Q带的蓝移。{CpFe(CO)Sn（大环）}单元（Cp：Cp或Cp*，大环：Pc或Nc）在和中形成紧密堆积的π-堆积二聚体，或在和中形成一维链，大环之间存在有效的π-π相互作用。这种堆积允许1/2自旋之间有强的反铁磁耦合。对于和中的孤立二聚体，磁相互作用可以用海森堡模型很好地描述，交换相互作用J / k = -78 K和-85 K，分别。和的磁行为可以用一个模型很好地描述，该模型包括来自反铁磁耦合的1/2二聚体（）和具有相邻原子之间交替反铁磁自旋交换的海森堡1/2链（）的贡献。化合物显示出大的二聚体内相互作用J / k = -54 K，而二聚体间交换相互作用基本上较弱，J / k = -6 K，而化合物显示出二聚体内自旋的强磁耦合（J / k = -170 K）以及二聚体间的强磁耦合（J / k = -40 K）。化合物{CpFe(CO)[Sn(TPP)]}（）在卟啉大环之间没有π-π相互作用，在这种情况下磁耦合较弱（韦斯温度为-5 K）。用氯化铟（III）酞菁制备类似的配合物得到{CpFe(CO)[In(Pc)]}（）。在该配合物中，铟（III）原子被还原，而不是酞菁大环，这解释了在4 - 295 K范围内的电子顺磁共振沉默。
