One-dimensional complexes extended by unbridged metal?metal bonds based on a HOMO?LUMO interaction at the dz2 orbital between platinum and heterometal atoms
One-dimensional complexes extended by unbridged metal?metal bonds based on a HOMO?LUMO interaction at the dz2 orbital between platinum and heterometal atoms
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基于铂和异金属原子之间 dz2 轨道上 HOMO?LUMO 相互作用的非桥接金属?金属键延伸的一维配合物
DOI：
10.1039/c6dt04515d
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发表时间：
2017
期刊：
影响因子：
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通讯作者：
Uemura Kazuhiro
中科院分区：
文献类型：
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作者：
Uemura Kazuhiro;Taoka Masahiro;谷脇旦,太田俊,岡崎雅明;松平将司,岡崎雅明;Uemura Kazuhiro
本文介绍了17个异金属一维化合物1-17的晶体结构，并根据漫反射光谱和其它物理测量结果讨论了它们的电子结构。化合物1-17包括两种在铂和杂金属原子之间的σ-型（dz 2）轨道上具有HOMO-LUMO相互作用的配合物，其中两种或三种金属通过金属-金属键规则排列。在[{PtRh（piam）2（NH3）2Cl2.5}2{Pt 2（piam）2（NH3）4}2]n（PF 6）6 n·2nMeOH·2nH 2 O（3，piam =新戊酰胺）中，铂和铑原子排列为-Pt-Rh-Pt-Pt-Pt-Pt-Rh-Pt-Cl-，具有混合价，其中未配对电子从一个Rh原子跳到另一个Rh原子。[{Rh 2（O2 CCF 3）4}{Pt 2（piam）2（NH3）4}2]n（CF 3CO 2）4 n·2nEtOH·2nH 2 O（6）具有-Pt-Pt-Rh-Rh-Pt-Pt-配向，导带（CB）和价带（VB）属于σ型轨道，CB和VB之间的带隙比其他类似物窄。具有-Pt-Pt-Ru-Ru-Pt-Pt-的[{Ru 2（O2 CCH 3）4}{Pt 2（piam）2（NH3）4}2]n（PF 6）4 n·4 nH 2 O（14）和具有-Rh-Rh-Pt-Cu-Pt-的[{Rh 2（O2 CCH 3）4}{Pt 2Cu（piam）4（NH3）4}]n（PF 6）2n（15）是顺磁链，其中每个重复单元的每个金属上存在一个或两个未成对电子。因此，该系统是多样的，在调制的电子结构，能带结构和预期的物理性质的基础上的独特的氧化态和氧化还原性能归因于金属-金属相互作用。
In this review, the crystal structures of seventeen heterometallic one-dimensional compounds 1–17 are shown, and their electronic structures are discussed based on the diffuse reflectance spectra and other physical measurements. Compounds 1–17 comprise two kinds of complexes with HOMO–LUMO interactions at σ-type (dz2) orbitals between platinum and heterometal atoms, where two or three kinds of metal are regularly aligned through metal–metal bonds. In [{PtRh(piam)2(NH3)2Cl2.5}2{Pt2(piam)2(NH3)4}2]n(PF6)6n·2nMeOH·2nH2O (3, piam = pivalamidate), the platinum and rhodium atoms are aligned as –Pt–Rh–Pt–Pt–Pt–Pt–Rh–Pt–Cl– with a mixed valence, where an unpaired electron hops from one Rh atom to another. [{Rh2(O2CCF3)4}{Pt2(piam)2(NH3)4}2]n(CF3CO2)4n·2nEtOH·2nH2O (6) with –Pt–Pt–Rh–Rh–Pt–Pt– alignment has a conduction band (CB) and a valence band (VB) attributed to σ-type orbitals, exhibiting narrower gaps between CB and VB than other analogues. [{Ru2(O2CCH3)4}{Pt2(piam)2(NH3)4}2]n(PF6)4n·4nH2O (14) with –Pt–Pt–Ru–Ru–Pt–Pt– and [{Rh2(O2CCH3)4}{Pt2Cu(piam)4(NH3)4}]n(PF6)2n (15) with –Rh–Rh–Pt–Cu–Pt– are paramagnetic chains, where one or two unpaired electrons reside at each metal per repeating unit. Thus, this system is diverse in modulating the electronic structures, band structures and the expected physical properties based on the unique oxidation states and redox properties attributed to the metal–metal interaction.