Fine tunable metal assemblies constrained by multidentate phosphine ligands
Fine tunable metal assemblies constrained by multidentate phosphine ligands
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DOI：
10.1016/j.ccr.2022.214581
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发表时间：
2022
影响因子：
20.6
通讯作者：
T. Tanase;Kanako Nakamae;Y. Ura;Takayuki Nakajima
中科院分区：
文献类型：
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作者：
T. Tanase;Kanako Nakamae;Y. Ura;Takayuki Nakajima
结构受限的多核金属组装体是原子级精确的纳米结构分子器件的迷人构建块，其具有由邻近金属中心的协同效应产生的电子、磁性、物理和催化性质的各种功能。金属组装体的精细结构和电子态的调整依赖于多齿引导和支撑配体的设计，并且旨在开发作为金属材料的分子微型物的低价金属组装体，具有由单个原子连接的一对软供体的那些，即，承载短咬合单元，是高度期望的。在这方面，本文综述了几十年来的研究，多核金属配合物的限制线性和支化的三，四，和多齿膦配体与短的咬距离之间的两个供体原子拥有P3，P4，和P6供体集。还解释了具有PCP、PNP、PAsP、PNNP和N（P3）供体组的混合供体膦的那些，因为卡宾、亚氨基氮和胂的杂软供体使得能够通过金属大环和螯合前体精细逐步合成杂金属组装体。不包括由非膦基多齿配体和由单膦和二膦支撑的多核络合物。这一贡献不仅集中在一维金属链，但在其他二维和三维拓扑结构的安排，特别是，突出了最近开发的Pt和Pd为基础的金属字符串组织的线性三-和四膦配体，光和电致发光的钴金属组件的线性，环，平面和多面体的金属安排，和铜氢化物多核配合物显示有吸引力的氢化物反应性。这些化合物的亚纳米到纳米尺度的积木将提供有用的平台，以开发进一步组装的纳米分子器件与结构和原子控制的合成策略。
Structurally constrained multinuclear metal assemblies are fascinating building blocks for atomically precise nano-structured molecular devices with a variety of functions from electronic, magnetic, photophysical, and catalytic properties arising from cooperative effects of proximate metal centers. Finely tuned structures and electronic states of metal assemblies are in debt to design of multidentate guiding and supporting ligands, and aiming to develop low valent metal assemblies as molecular miniatures of metallic materials, those with a pair of soft donors connected by a single atom, namely, bearing short bite units, are highly desired. In this regard, this review surveys the studies over a couple of decades on multinuclear metal complexes constrained by linear and branched tri-, tetra-, and polydentate phosphine ligands with short bite distances between the two donor atoms possessing P3, P4, and P6donor sets. Those with mixed donor phosphines having PCP, PNP, PAsP, PNNP, and N(P3) donor sets, are also explained because the hetero soft donors of carbene, imino-nitrogen, and arsine enable fine stepwise syntheses of heterometal assemblies through metallomacrocyclic and metallocage precursors. Multinuclear complexes supported by non-phosphino multidentate ligands and by mono- and diphosphines are not included. This contribution focuses not only on 1D metal chains but on other 2D and 3D topological arrangements, and in particular, highlights the recently developed Pt and Pd based metal strings organized by linear tri- and tetraphosphine ligands, photo- and electroluminescent coinage metal assemblies in linear, ring, planar, and polyhedral metal arrangements, and copper hydride multinuclear complexes showing attractive hydride reactivity. These compounds of subnano- to nano-scaled building blocks will provide useful platforms to develop further assembled nano-molecular devices with structurally and atomically controlled synthetic strategies.