Murai Masahito, Ono Masanori, Tanaka Yuya, Akita Munetaka
Laboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan.
ACS Org Inorg Au. 2024 Jul 15;4(5):504-516. doi: 10.1021/acsorginorgau.4c00021. eCollection 2024 Oct 2.
Four dinuclear organometallic molecular wire complexes with diethynylmetalloporphyrin linkers , [5,15-bis{MCp*(dppe)ethynyl}-10,20-diarylporphinato]M' (Cp* = η-CMe; dppe = 1,2-bis(diphenylphosphino)ethane; M/M' = Fe/Zn ( ), Ru/Zn ( ), Fe/Ni ( ), Ru/Ni ( ); aryl = 3,5-di--butylphenyl), are synthesized and characterized by NMR, CV, UV-vis-NIR, and ESI-TOF mass spectrometry techniques. Electrochemical investigations combined with electronic absorption spectroscopic studies reveal strong interactions among the electron-donating, redox-active MCp*(dppe) termini and the metalloporphyrin moieties. The monocationic species of the four complexes obtained by chemical oxidation have been characterized as mixed-valence Class II/III or Class III compounds according to the Robin-Day classification despite the long molecular dimension (>1.5 nm), as demonstrated by their intense intervalence charge transfer bands (IVCT) in the near IR region. DFT calculations indicate large spin densities on the metalloporphyrin moieties. Furthermore, the wirelike performance can be finely tuned by coordination of appropriate nitrogen donors to the axial sites of the metalloporphyrin.
合成了四种带有二乙炔基金属卟啉连接体的双核有机金属分子线配合物，即[5,15-双{MCp*(二苯基膦基乙炔基)}-10,20-二芳基卟吩]M'（Cp* = η-CMe；二苯基膦基乙炔基 = 1,2-双(二苯基膦基)乙烷；M/M' = Fe/Zn ( )、Ru/Zn ( )、Fe/Ni ( )、Ru/Ni ( )；芳基 = 3,5-二叔丁基苯基），并通过核磁共振、循环伏安法、紫外-可见-近红外光谱以及电喷雾飞行时间质谱技术对其进行了表征。电化学研究与电子吸收光谱研究相结合，揭示了给电子的、具有氧化还原活性的MCp*(二苯基膦基乙炔基)末端与金属卟啉部分之间的强相互作用。通过化学氧化得到的这四种配合物的单阳离子物种，根据罗宾-戴分类法被表征为II/III类或III类混合价化合物，尽管分子尺寸较长（>1.5 nm），这一点可由它们在近红外区域强烈的价间电荷转移带（IVCT）得到证明。密度泛函理论计算表明金属卟啉部分存在较大的自旋密度。此外，通过使合适的氮供体与金属卟啉的轴向位点配位，可以对这种线状性能进行精细调节。
