Designs of 3-Dimensional Networks and MOFs Using Mono- and Polymetallic Copper(I) Secondary Building Units and Mono- and Polythioethers: Materials Based on the Cu–S Coordination Bond

Abstract

This mini-review surveys 23 structures of 3D coordination polymers built upon mono-, di-as well as cyclic and acylic polythioethers. An emphasis is put on the Secondary Building Units (SBU) and the physical properties. Importantly, the key feature is that the dominant SBU is not the rhomboid (Cu 2 X 2 S 4 ), but an inorganic polymer containing at least the chain of the type (CuX) n . In the latter type of SBU, these chain formations are observed for X = I, but predominantly for X = CN. In addition, a large portion of the surveyed materials exhibit rich photophysical properties, but on several occasions, these materials exhibit properties often attributed to MOFs, mainly solvent exchange.

Assembly of Coordination Polymers Using Thioether‐Functionalized Octasilsesquioxanes: Occurrence of (CuX)n Clusters (X=Br and I) within 3D‐POSS Networks

“…I). Thus, a wide range of networks (one, two and three‐dimensional) containing, among others, Cu 2 X 2 rhomboids, cubane‐type (Cu 4 X 4 ), hexanuclear (Cu 6 I 6 ) and even octanuclear (Cu 8 I 8 ) clusters as connecting nodes have been explored …”

Control of Structures and Emission Properties of (CuI)n 2-Methyldithiane Coordination Polymers

“…The design of coordination polymers with a predictable secondary building unit (SBU) and dimensionality is a quasi-impossible task but the quest remains of great interest for the discovery of new materials with desired properties such as gas adsorption, [1][2][3][4][5][6][7][8][9] sensing, [10][11][12][13][14][15] thermochromism, [16][17][18][19] magnetism, [20][21][22][23][24] conductivity, [25][26][27][28] redox-activity, 29,30 catalysis, 13,[31][32][33] nonlinear optical behavior 34,35 and luminescence. 8,[36][37][38][39][40] Recent reviews on CPs formed by mono-and dithioethers with CuX salts (X = Cl, Br, I) [41][42][43][44][45][46]…”

Completely Unexpected Coordination Selectivity of Copper Iodide for Thioether Over Ethynyl

“…Again, this situation was not observed in L2 (see Fig. 9 and Table 3) but was noted for other CP exhibiting the SC 6 H 4 R moiety (R = alkyl group) on the thioether ligands [47][48][49]. Moreover, ideally one could comments on the comparison of the Cu-S and Cu(η 2 -C≡C) bond energies.…”

“…1) with a general formula ([Cu 4 I 4 ]L1 • solvent) n (solvent = MeCN, EtCN) [23,24]. This trait is somewhat unusual since the structure of the SBU is highly variable going from the rhomboid Cu 2 I 2 , to the closed and open cubane Cu 4 I 4 , to the staircase Cu 4 I 4 , to the hexagonal Cu 6 I 6 , to the closed side-fused dicubane Cu 8 I 8 , to the polymeric staircase (Cu 2 I 2 ) n geometries, just to state a few, and that a slight structural modification of the bridging dithioether ligand can lead to a complete change in SBU and even CP dimensionality [47][48][49]. Third, the L2 ligand crystalizes side-by-side with an astonishing resemblance with the crystal structure of L2 itself.…”

“…Any combination of the low-energy electronic transitions (i.e. HOMO → LUMO, HOMO-1 → LUMO, HOMO → LUMO + 1) creates metal-halide-to-ligand charge transfer excited states M/XLCT, an outcome considered common in CuX-dithoether assemblies (X = halide) [47][48][49]. Similarly, the LSOMO and HSOMO exhibit atomic contributions respectively localized mainly in one of the Cu 4 I 4 Fig.…”