Nazarov Dmitry I, Faraonov Maxim A, Nations Sean M, Gutsev Lavrenty G, Yakushev Ilya A, Kuzmin Alexey V, Khasanov Salavat S, Otsuka Akihiro, Yamochi Hideki, Kitagawa Hiroshi, Konarev Dmitri V
Federal Research Center of Problems of Chemical Physics and Medical Chemistry RAS, Chernogolovka, Moscow region 142432, Russia.
National Energy Technology Laboratory, United States Department of Energy, Pittsburgh, Pennsylvania 15236, United States.
Inorg Chem. 2024 Dec 2;63(48):22677-22687. doi: 10.1021/acs.inorgchem.4c02477. Epub 2024 Sep 17.
A series of hybrids comprising two metal (Mn, Fe, and In) tetraphenylporphyrins axially substituted with anionic bidentate -thioindigo ligands (TI) were obtained. Substitution of the axial chloride anion by an oxygen atom of the dye forms short M-O bonds. Crystalline binuclear assemblies (TI)·{[MnTPP]·[MnTPP]}·CHCl ( = 2 for or 1 for ) and (TI){[MTPP]}·CHCl (M = Fe and = 2 for , M = In and = 1 for ) were synthesized. The thioindigo (TI) dianion and metal (Fe and In) atoms in TPPs maintain their initial charge states during the formation of and , allowing the separation of paramagnetic Fe or diamagnetic In ions by a diamagnetic TI bridge. Strong antiferromagnetic coupling is observed between Fe ( = 5/2) centers in complex . Partial reduction of Mn to Mn occurs upon the formation of and , leading to assemblies containing three paramagnetic centers: Mn ( = 5/2), Mn ( = 2), and TI radical anion ( = 1/2). Orthogonal arrangement of TPP and TI molecules in provides strong ferromagnetic coupling. Weak antiferromagnetic coupling is realized in due to the rotation of the TI bridge.
得到了一系列由两个金属（锰、铁和铟）四苯基卟啉轴向被阴离子双齿硫靛配体（TI）取代而成的杂化物。染料的氧原子取代轴向氯阴离子形成短的M - O键。合成了晶体双核组装体（TI）·{[MnTPP]·[MnTPP]}·CHCl（对于 为2，对于 为1）和（TI）{[MTPP]}·CHCl（M = 铁，对于 为2；M = 铟，对于 为1）。在 和 的形成过程中，硫靛（TI）二价阴离子和卟啉中的金属（铁和铟）原子保持其初始电荷状态，使得顺磁性的铁离子或抗磁性的铟离子通过抗磁性的TI桥得以分离。在配合物 中观察到铁（ = 5/2）中心之间有强反铁磁耦合。在 和 的形成过程中，锰部分还原为锰，导致组装体包含三个顺磁性中心：锰（ = 5/2）、锰（ = 2）和TI自由基阴离子（ = 1/2）。 中TPP和TI分子的正交排列提供了强铁磁耦合。由于TI桥的旋转， 中实现了弱反铁磁耦合。
