Reaction of AgOTf with a tetraphosphine, rac-bis[(diphenylphosphinomethyl)- phenylphosphino]methane (rac-dpmppm), afforded [Ag₄(rac-dpmppm)₂](TfO)₄ (3) which consists of zigzag-arrayed tetranuclear silver(I) ions supported by syn-arrangement of two enantiomeric (RR/SS) dpmppm ligands. Complex 3 readily reacted with XylNC (Xyl = 2,6-dimethylphenyl) to give [Ag₄(rac-dpmppm)₂(XylNC)₂](TfO)₄ (4), where two terminal isocyanides attach to the outer Ag sites. Complex 3 has been shown a good precursor for PtAgAgPt mixed metal array as incubation of 3 with trans-[Pt(CCPh)₂(PPh₃)₂] yielded [Ag₂Pt₂(CCPh)₄(rac-dpmppm)₂](TfO)₂ (5). Two trans-Pt(CCPh)₂ units are incorporated into the terminal positions in a site-selective fashion and the PtAgAgPt tetranuclear core also adopts a zigzag array supported by syn-arrangement of two rac-dpmppm ligands. The d⁸ and d¹⁰ closed-shell mixed metal centers of 5 exhibited an intense photoluminescence at 534 nm, mainly from an unsymmetric triplet state generated by charge transfer transitions from ligand (acetylide π) to metal centers (Ag₂ and PtAg s/p_σ), ³LMCT, and to ligands (acetylide π* and dpmppm), ³LLCT. The present results provide fundamental and useful information to construct multinuclear closed-shell metal alignments by utilizing polyphosphine ligands.

AgOTf与四膦，rac-双[（二苯基膦基甲基）-苯基膦]甲烷（rac -dpmppm）反应，得到[Ag ₄（rac -dpmppm）₂ ]（TfO）₄（3），它由曲折排列的四核银组成（I）由两个对映体（RR / SS）dpmppm配体的顺式排列支持的离子。配合物3容易与XylNC（Xyl = 2,6-二甲基苯基）反应生成[Ag ₄（rac -dpmppm）₂（XylNC）₂ ]（TfO）₄（4），两个末端异氰酸酯连接到外部Ag位点。配合物3已显示为PtAgAgPt混合金属阵列的良好前体，因为将3与反式-[Pt（C CPh）₂（PPh ₃）₂ ]孵育可产生[Ag ₂ Pt ₂（C CPh）₄（rac -dpmppm）₂ ]（TfO）₂（5）。两个反式-Pt（C CPh）₂单元以位点选择性方式并入末端位置，并且PtAgAgPt四核核心也采用由两个rac -dpmppm配体的顺式排列。d ⁸和d ¹⁰的5的闭壳混合金属中心在534 nm处显示出强烈的光致发光，主要是由于从配体（乙炔π）到金属中心（Ag ₂和PtAg s / p ）的电荷转移跃迁产生的不对称三重态_σ），³ LMCT，配体（乙酰胺π*和dpmppm），³ LLCT。本结果为利用多膦配体构建多核闭壳金属比对提供了基础和有用的信息。