Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093, USA.
Inorg Chem. 2013 Jul 15;52(14):7862-72. doi: 10.1021/ic302840x. Epub 2013 Jun 25.
An array of coordination-driven supramolecular metal-ligand clusters has been synthesized using polytopic phosphine ligands and coinage metals (Cu(+), Ag(+), Au(+)). Rigid 3-fold or 2-fold symmetric phosphine ligands have been prepared: 1,3,5-tris((4-(diphenylphosphino)ethynyl)phenyl)benzene) (tppepb, L(1)), 1,4-bis((diphenylphosphino)ethynyl)benzene (1,4-dppeb, L(2)), 1,3-bis((diphenylphosphino)ethynyl)benzene (1,3-dppeb, L(3)), 2,6-bis((diphenylphosphino)ethynyl)pyridine (2,6-dppep, L(4)), and 1,5-bis((diphenylphosphino)ethynyl)naphthalene (1,5-dppen, L(5)). Self-assembly of these ligands with coinage metals produces four different types of metal-ligand clusters, or in some cases coordination polymers, depending on number and relative geometry of the phosphine donor atoms. Supramolecular tetrahedral clusters of the formula M4(L(1))4I4 (M = Cu(+), Ag(+), Au(+)) were obtained with the tppepb ligand, encapsulating solvent molecules (either CH2Cl2 or DMF) as guests within the central cavity of the clusters. The ligands 1,3-dppeb (L(3)) and 2,6-dppep (L(4)) give achiral, triple-stranded, dinuclear mesocates with the formula M2(L)3I2 (M = Cu(+) or Au(+)). In contrast, the ligand 1,4-dppeb (L(2)) generates a triple-stranded, dinuclear helicate with Cu(+), but a coordination polymer with Au(+) (both with the empirical formula M2(L(2))3I2). Finally, coordination polymers were obtained from 1,5-dppen (L(5)) with Cu(+). The clusters have been fully characterized by single crystal X-ray crystallography, high-resolution mass spectrometry, (1)H NMR, and (31)P NMR.
已经使用多齿膦配体和铜 (+)、银 (+)、金 (+) 合成了一系列配位驱动的超分子金属 - 配体簇。已经制备了刚性 3 重或 2 重对称膦配体：1,3,5-三((4-(二苯膦基)乙炔基)苯基)苯)（tppepb，L(1)），1,4-双((二苯膦基)乙炔基)苯（1,4-dppeb，L(2)），1,3-双((二苯膦基)乙炔基)苯（1,3-dppeb，L(3)），2,6-双((二苯膦基)乙炔基)吡啶（2,6-dppep，L(4)）和 1,5-双((二苯膦基)乙炔基)萘（1,5-dppen，L(5)）。这些配体与贵金属的自组装产生了四种不同类型的金属 - 配体簇，或者在某些情况下是配位聚合物，具体取决于膦供体原子的数量和相对几何形状。使用 tppepb 配体获得了化学式为 M4(L(1))4I4（M = Cu(+)、Ag(+)、Au(+)）的四面体超分子簇，将溶剂分子（无论是 CH2Cl2 还是 DMF）作为客体包封在簇的中心腔内。配体 1,3-dppeb（L(3)）和 2,6-dppep（L(4)）给出非手性的三重股双核介离子，化学式为 M2(L)3I2（M = Cu(+)或 Au(+)）。相比之下，配体 1,4-dppeb（L(2)）生成三重股双核螺旋体与 Cu(+)，但与 Au(+)生成配位聚合物（两者的经验式均为 M2(L(2))3I2）。最后，从 1,5-dppen（L(5)）获得了与 Cu(+)配位的聚合物。这些簇已通过单晶 X 射线晶体学、高分辨率质谱、(1)H NMR 和 (31)P NMR 进行了全面表征。
