Metal-to-Ligand Ratio Effect on the Size of Copper Iodide and Copper Bromide Clusters in 1,4-Bis(cyclohexylthio)butane-Spanned Coordination Polymers

Abstract

International audienc

From Short-Bite Ligand Assembled Ribbons to Nanosized Networks in Cu(I) Coordination Polymers Built Upon Bis(benzylthio)alkanes (BzS(CH2)nSBz; n = 1–9)

“…The X-ray analysis shows the formation of a 1D CP {Cu(μ 2 -I) 2 Cu}(μ-L1) 2 ] n (CP1) (Figure 1, Scheme ] n , formed by the self-assembly of CuI with the carbonyl-functionalized dithioether 2-(cyclohexythio)-1-thiomorpholino-ethanone ligand. 33,42,43 We also recently described the structure of the 1D CP [{Cu(μ 2 -I) 2 Cu}{μ 2 -methyldithia-ne} 2 ] n , spanned by rigid 2-methyldithiane heterocycles featuring a CH 2 SCH(Me)SCH 2 motif, in which like in L1, the two S donor sites are separated by a single C atom as a spacer. 44 However, a closer look reveals the coexistence of two independent ribbons (A and B) running along the a axis.…”

“…At first glance, this 1D architecture does not seem spectacular since it has been previously reported for several other flexible RS­(CH 2 ) n SR ligands and CPs such as [{Cu­(μ 2 -I) 2 Cu}­{μ-CyS­(CH 2 ) 4 SCy} 2 ] n ( d Cu ··· Cu = 3.0089(15) Å) and [{Cu­(μ 2 -I) 2 Cu}­{μ-PhS­(CH 2 ) 5 SPh} 2 ] n ( d Cu ··· Cu = 3.0089(15) Å), as well as for [{Cu­(μ 2 -I) 2 Cu}­{μ-C 6 H 11 CH 2 SCH 2 C­(O)­NC 4 H 8 S} 2 ] n , formed by the self-assembly of CuI with the carbonyl-functionalized dithioether 2-(cyclohexythio)-1-thiomorpholino-ethanone ligand. ,, We also recently described the structure of the 1D CP [{Cu­(μ 2 -I) 2 Cu}­{μ 2 -methyldithiane} 2 ] n , spanned by rigid 2-methyldithiane heterocycles featuring a CH 2 SCH­(Me)­SCH 2 motif, in which like in L1 , the two S donor sites are separated by a single C atom as a spacer . However, a closer look reveals the coexistence of two independent ribbons ( A and B ) running along the a axis.…”

“…These species exhibit generally intense and structureless bands spreading from 430 to 730 nm at room temperature. ,,− ,,,,− The photophysical characterization of the thioether-containing cubanes and related species included in 0D–3D materials was extracted from more focused studies from the literature, and includes the emission lifetimes (τ e ) at 298 and 77 K, which generally range from 0.2 to 16 μs. A table containing these reported photophysical data is provided in Table S7. ,,,− ,,,,,,,, The cubane-containing CPs in this series make no exception (Figure ) with the small difference that some bands expand beyond 700 nm (near-IR).…”

“…A table containing these reported photophysical data is provided in Table S7. 32,34,61,[85][86][87][88][89][90]35,36,42,44,46,48,53,59 The cubane-containing CPs in this series make no exception (Figure 29) with the small difference that some bands expand beyond 700 nm (near-IR). CP4, CP8, CP11, CP15, CP19, and CP23 exhibit τ e 's values in the predicted range (Table 2; 1.8 ≤ τ e ≤ 15 μs).…”

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

“…This 3D polymer is weakly luminescent. This characteristic is common for rhomboid-containing species [33][34][35][36][37]. Moreover, this very low intensity luminescence property is more pronounced for CuX-containing materials when X = Cl and Br [34].…”