SELF-ASSEMBLY OF CATIONIC, TETRANUCLEAR, PT(II) AND PD(II) MACROCYCLIC SQUARES - X-RAY CRYSTAL-STRUCTURE OF [PT2+(DPPP)(4,4'-BIPYRIDYL)2(-)OSO(2)CF(3)](4)
SELF-ASSEMBLY OF CATIONIC, TETRANUCLEAR, PT(II) AND PD(II) MACROCYCLIC SQUARES - X-RAY CRYSTAL-STRUCTURE OF [PT2+(DPPP)(4,4'-BIPYRIDYL)2(-)OSO(2)CF(3)](4)
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DOI：
10.1021/ja00128a015
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发表时间：
1995-06-14
影响因子：
15
通讯作者：
ARIF, AM
中科院分区：
文献类型：
--
作者：
STANG, PJ;CAO, DH;ARIF, AM
报道了一系列独特的阳离子、四核、铂(II)和钯(II)基大环方的制备、表征和一些化学性质。在有机溶剂中，多种双齿配体(联吡啶、重氮苯、二氰基苯和二氰基联苯)在有机溶剂中与正方平面的顺双膦铂和钯双三氟酸盐配合物在室温下相互作用，通过自组装得到高产率的分子方块。所有分子方块都是坚固的空气和水稳定的微晶固体，分解点大多在200摄氏度以上。它们通常可溶于极性有机溶剂，但不溶于水或非极性溶剂，如戊烷、甲苯和乙醚。基于氰基的大环在溶液中具有很强的流动性，而BiPY及其相关体系则更稳定。1，5-二羟基萘的邻质子和间质子发生了浓度相关的化学位移，表明了主客体相互作用和包结现象。报道了分子方形[(Dppp)Pt(Bipy)](8+)(4)8(-)Oso(2)Cf(3)(15a)，以及双核双氰苯配合物25和[(Dppp)M(吡嗪)](2+)2(-)Oso(2)Cf(3)(M=Pt，Pd)配合物20a，b的X射线晶体结构。
The preparation, characterization, and some chemistry of a series of unique cationic, tetranuclear, Pt(II)- and Pd(II)-based macrocyclic squares are reported. A variety of bidentate ligands (bipyridine, diazapyrene, dicyanobenzene, and dicyanobiphenyl) are interacted with the square-planar cis-bis(phosphine) Pt and Pd bis(triflate) complexes in organic solvents at room temperature, resulting in molecular squares in high isolated yields via self-assembly. All molecular squares are robust air- and water-stable microcrystalline solids with decomposition points mostly above 200 degrees C. They are generally soluble in polar organic solvents but not in water or nonpolar solvents like pentane, toluene, and ether. The cyano-based macrocycles are highly fluxional in solution, whereas the bipy and related systems are more stable. Concentration-dependent chemical shifts are observed for the ortho and meta protons of 1,5-dihydroxynaphthalene, indicating host-guest interactions and inclusion phenomena. X-ray crystal structures are reported for the molecular square [(dppp)Pt(bipy)](8+)(4)8(-)OSO(2)CF(3) (15a), as well as a dinuclear dicyanobenzene complex 25 and the [(dppp)M(pyrazine)](2+)2(-)OSO(2)CF(3) (M = Pt, Pd) complexes 20a,b.