Correlation between structures and physical properties for pi-conjugated multinuclear complexes

在7T共轭多核过渡金属配合物的研究中，研究核间电子相互作用的结构和强度与物理性质之间的关系是非常重要的。本研究合成了含二茂铁、钴二硫和联吡啶的新型齐聚化合物和聚合物，并研究了它们的结构与氧化还原、光学和磁性的关系。合成了新的偶氮桥联二茂铁三聚物FC-FC‘-N=N-FC和FC-N=N-FC’-N=N-FC，其中FC和FC‘分别是指(ETA^5-C5H5)Fe(ETA^5-C5H4-)和Fe(ETA^5-C5H4-)2。其电化学性质和光学性质表明，其混合价电子结构可分别表示为FC^+-N_2-FC，FC^+-N_2-FC‘-N_2-FC^+和FC^+-FC’-N_2-FC，FC^+-FC‘-N_2-FC^+。混合价态IT带的溶剂效应不能仅用参数…来解释更多的S在Marcus-Hush理论中的观点，表明在混合价状态下的电子交换过程中应考虑溶剂作为给体或受体的性质。邻二茂铁、间二茂铁和对二茂铁乙炔的氧化还原性质和光学性质表明，当二茂铁单元位于对位时，它们之间的电子相互作用最显著。通过考虑O、m和p位上二茂铁单元之间的全部电子相互作用的贡献，可以半定量地解释六轴(二茂铁乙炔)苯的物理性质。通过钴二硫杂环化合物与M(CO)3PY3反应，合成了新的Co-M-Co(M=Mo，W)簇合物，并测定了它们的X射线晶体结构。它们的物理性质和它们的还原形式表明两个钴中心金属之间存在着强烈的电子相互作用。合成了以偶氮苯为连接剂的双(联吡啶)配体TPY-AB-TPY及其Rh、Ru和Co双核配合物。揭示了它们的光异构化反应和氧化还原性质。较少

In the research of 7t-conjugated multinuclear transition metal complexes, it is important to investigate the correlation between structures and strength of intermuclear electronic interactions with physical properties. In this study, we have synthesized new oligomeric and polymeric compounds involving ferrocene, cobaltadithiolene and terpyridine complexes, and investigated the correlation between their structures and redox, optical and magnetic properties.New azo-bridged ferrocene trimers, Fc-Fc'-N=N-Fc and Fc-N=N-Fc'-N=N-Fc, where Fc and Fc' refer to (eta^5-C_5H_5)Fe(eta^5-C_5H_4-) and Fe(eta^5-C_5H_4-)_2, respectively, were synthesized. Their electrochemical and optical properties indicate that the electronic structures of their mixed-valence states can be expressed as Fc^+-N_2-Fc'-N_2-Fc, Fc^+-N_2-Fc'-N_2-Fc^+, and Fc^+-Fc'-N_2-Fc, Fc^+-Fc' -N_2-Fc^+, respectively. The solvent effect of the IT band in their mixed-valence states on nu_<max> cannot be interpreted only by the parameter … More s in the Marcus-Hush theory, indicating that the nature of the solvent as donor or acceptor should be taken into account in the electron-exchange process in the mixed-valence states.Redox properties and optical properties of o, m, and p-bis (ferrocenylethynyl) benzene indicate that the electronic interaction between ferrocene units is most significant when they locate at para position. Physical properties of hexaxis (ferrocenylethynyl) benzene can be semi-quantitatively interpreted by considering the contribution of all electronic interaction between ferrocene units at o, m and p-positions.New Co-M-Co (M=Mo, W) cluster complexes were synthesized by the reaction of cobaltadithiolene complex with M(CO)_3py_3 and their X-ray crystallographic structures determined. Physical properties of them and their reduced forms indicate the existence of strong electronic interaction between two Co sites via the central metal.A new bis (terpyridine) ligand with azobenzene as the linker, tpy-AB-tpy and their Rh, Ru and Co dinuclear complexes were synthesized. Their photoisomerization reactions and redox properties were revealed. Less