Supramolecular Assembly of Multinuclear Silver(I) Complexes Containing Alkyl or Aromatic Ethynide.

摘要

This thesis presents a systematic synthetic and structural study of silver(I) ethynide complexes employing a new kind of polynuclear metal-ligand supramolecular synthon for the construction of silver(I) coordination networks.;We have developed different crystallization techniques in the supramolecular assembly of the Ph--C≡C⊃Agn ( n = 3, 4, 5) metal-ligand synthon and various anions to obtain an infinite silver(I) chain in 4AgC≡CPh·10AgCF3CO 2·8DMSO (4), silver(I) layers in 2AgC≡CPh·AgNO 3 (2) and AgC≡CPh·AgNO3 (1), a thick silver(I) column in 5AgC≡CPh·AgNO3·AgCF 3SO3·2DMSO (5), and cationic silver(I) columns in [Ag5(PhC≡C)4(DMSO)2]X (X = ClO4, BF4, PF6, AsF6 and SbF 6) (3).;The above results encouraged us to carry out further investigation through variation of the nature or position of substituents (F, Cl, Br, I, Me, C(=O)CH 3, NO2 and C≡N) on the aromatic ring to yield silver(I) chain, column, ribbon, layer, and 3D porous coordination polymers, as well as a polyhedral silver(I) column. For example, an olive-shaped Ag15 core exists in [(NO3) Ag15(C≡CC6H 4F--2)10](NO3)4 (15), in which the encapsulated nitrate ion acts as a template for the formation of the Ag15 cluster. Such Ag15 clusters are then joined together to form a polymeric silver(I) chain. Peanut-shaped silver(I) double cages, each formed from two nitrate ions encapsulated within a Ag26 cage, are linked together to form a polyhedral silver(I) chain in [(NO3)2 Ag26(C≡CC6H 4Me--2)16](NO3)8 (23).;The silver(I)-ethynide supramolecular synthon participating in silver(I)-vinyl and silver(I)-cyano interactions plays an important role to generate 2-D silver-organic networks in AgC≡CCH2OC6H4(CH=CH 2--2) · 6AgCF3CO2 · 3H2O (31) and 2AgC≡CC6H4(C≡N-- 4) · 4AgO2CCF3 · 2DMSO · H2O (36).;The pi-electron system of polycyclic aromatic hydrocarbons (PAHs) is known to be capable of bonding to metal ions. The exploitation of such cation--pi interactions provides a potentially fruitful approach to building novel solid-state architectures. Our conceived idea is to investigate the pi-pi stacking and silver(I)-heteroaromatic interactions for the construction of coordination polymers using the R--C≡C⊃Agn ( n = 4, 5; R = naphthalenylethynide or quinolinylethynide) supramolecular synthon. In the compounds (C10H7C≡C-- 1)Ag · 3AgO2CCF3 · 3H2O (38) and (C10H7C≡C-- 2)Ag · 3AgO2CCF3 · 2H2O · MeCN (39), silver-pi interaction has been successfully introduced into silver(I)--ethynide systems. Intermolecular pi--pi interaction contributes to the assembly of supramolecular synthons in compounds Ag( 1--NC9H6C≡C--2) · 3AgO2CCF3 · 3H2O (44) and Ag(1--NC9H6C≡C-- 4) · 3AgO2CCF3 · 2H2O (47).;Traditionally, anion templates are used in a facile approach for the synthesis of high-nuclearity silver(I) clusters. The cluster nuclearity can be controlled by adjusting the size of the templating anions and by using different alkynyl ligands. After using the giant polyoxometalates (POMs) anion, Mo6O228-, to form a large Ag60 alkynyl cluster, we have developed another approach to synthesize high-nuclearity silver(I) clusters. Generation of a Ag38 ethynide cluster from a rhombic dodecahedral Ag14 ethynide cluster as precursor occurs in solution via a re-assembly process that involves transformation of the encapsulated chloride template in the small cluster into a pseudo- Oh Cl6Ag8 core in the giant cluster complexes Ag38Cl6(tBuC≡C) 20(ClO4)12 · Et2O (48 ) and Ag38Cl6(chxC≡C)20(ClO 4)12 · 1.5Et2O (49).