Coordination Networks through the Dimensions:  From Discrete Clusters to 1D, 2D, and 3D Silver(I) Coordination Polymers with Rigid Aliphatic Amino Ligands

Abstract

The use of a ligand directed strategy in the assembly of discrete clusters, 1D chains, 2D layers, and 3D networks using aliphatic N-donor ligands has been investigated. The ligands are a family of amines with rigid backbones [cis,cis-1,3,5-triaminocyclohexane (cis-tach), cis,trans-1,3,5-triaminocyclohexane (trans-tach), cis-1,3-diaminocyclohexane (cis-dach), and cis-3,5-diaminopiperidine (cis-dapi)], and their complexation with Ag(I) salts results in a diverse set of architectures with the following compositions: [Ag3(cis-tach)2]F3.4CH(3)OH.0.5H2O (1), [Ag3(cis-tach)2]F3.6H2O (2), ([Ag(cis-dach)]ClO4)n (3), ([Ag(cis-tach)]NO3)n (4), ([Ag(trans-tach)]PF6)n(5), and ([Ag(cis-dapi)]CF3SO3)n (6). Structural analysis shows that compounds 1 and 2 are discrete M(3)L(2) cage-type clusters with varying solvent molecule content. Short Ag...Ag contacts (3.021(8) A) are observed to dimerize discrete units in compound 2. Compound 3 is a 1D zigzag chain formed by coordination to the two primary amines of cis-dach, whereas the tridentate ligands in compounds 4 and 5 (cis-tach and trans-tach, respectively) are able to form tubular architectures by virtue of their ability to "wrap" round the channel walls. An infinite 2D coordination network is demonstrated by compound 6, in which the three coplanar amino donors of cis-dapi coordinate to the trigonal planar Ag(I) ions to form a layered structure of 6(3) topology. These are compared with a previously reported 3D structure, ([Ag(trans-tach)]NO3)n (7), that belongs to this family of architectures.

Variability in the Structures of Luminescent [2‐(Aminomethyl)pyridine]silver(I) Complexes: Effect of Ligand Ratio, Anion, Hydrogen Bonding, and π‐Stacking

“…This is because of the flexibility in its coordination sphere and the ease with which it varies the coordination number. [9][10][11][12][13] Many silver coordination architectures are readily obtainable through slight variations in ligand and/or anion and include discrete, small molecules, supramolecular arrays, and 1-, 2-, and 3-dimensional coordination networks. [13][14][15][16][17] Several systematic studies of the structural dependence on anions have been nicely demonstrative of the diversity possible with small changes in counterion properties such as coordinating or hydrogen-bonding ability.…”

Self‐Assembly and Characterization of Grid‐Type Copper(I), Silver(I), and Zinc(II) Complexes

“…A variety of architectural types are known, such as, for example, inorganic double, [1][2][3][4][5] triple, [4,5] and quadruple [6] helicates, rotaxanes, [7][8][9] clusters, [10][11][12] racks, [13] cages, [14][15][16] grids [17][18][19][20][21][22][23][24][25][26][27][28] etc., based on ligand design and on the application of suitable coordination geometries for the assembly process. Among them, there is an increasing interest in grid-shaped complexes based on ligands containing oligopyridine-type groups and various transition metal ions.…”

Thermal, solution and structural studies of a 3D Ag(I) coordination polymer with various Ag-Ag bonds, [Ag3(μ-Hbtc)(μ-H2btc)]n

“…The Ag-Ag interactions in compound 1 are longer than the Ag-Ag distances in similar dinuclear complexes (i.e., 2.704(2), 2.669(1), and 2.726(1) ) and slightly shorter than those in the polymeric structure [30][31][32][33][34][35][36][37][38]. These relatively short Ag-Ag bonds may be considered only d 10 ···d 10 noncovalent interactions [30][31][32][33][34][35][36][37][38]. Various types of Ag-Ag interactions and hydrogen bonding (Table 3 and Fig.…”