Construction of (CuX)_2n Cluster-Containing (X = Br, I; n = 1, 2) Coordination Polymers Assembled by Dithioethers ArS(CH₂)_mSAr (Ar = Ph, p-Tol; m = 3, 5): Effect of the Spacer Length, Aryl Group, and Metal-to-Ligand Ratio on the Dimensionality, Cluster Nuclearity, and the Luminescence Properties of the Metal–Organic Frameworks

Abstract

Reaction of CuI with bis(phenylthio)propane in a 1:1 ratio yields the two-dimensional coordination polymer [{Cu(μ(2)-I)(2)Cu}{μ-PhS(CH(2))(3)SPh}(2)](n) (1). The 2D-sheet structure of 1 is built up by dimeric Cu(2)I(2) units, which are connected via four bridging 1,3-bis(phenylthio)propane ligands. In contrast, treatment of 2 equiv of CuI with 1,3-bis(phenylthio)propane in MeCN solution affords in a self-assembly reaction the strongly luminescent metal-organic 2D-coordination polymer [Cu(4)I(4){μ-PhS(CH(2))(3)Ph}(2)](n) (2), in which cubane-like Cu(4)(μ(3)-I)(4) cluster units are linked by the dithioether ligands. The crystallographically characterized one-dimensional (1D) compound [{Cu(μ(2)-Br)(2)Cu}{μ-PhS(CH(2))(3)SPh}(2)](n) (3) is obtained using CuBr. The outcome of the reaction of PhS(CH(2))(5)SPh with CuI also depends of the metal-to-ligand ratio employed. Mixing CuI and the dithioether in a 2:1 ratio results in formation of [Cu(4)I(4){μ-PhS(CH(2))(5)Ph}(2)](n) (4) in which cubane-like Cu(4)(μ(3)-I)(4) clusters are linked by the bridging dithioether ligand giving rise to a 1D necklace structure. A ribbon-like 1D-polymer with composition [{Cu(μ(2)-I)(2)Cu}{μ-PhS(CH(2))(5)SPh}(2)](n) (5), incorporating rhomboid Cu(2)I(2) units, is produced upon treatment of CuI with 1,5-bis(phenylthio)pentane in a 1:1 ratio. Reaction of CuBr with PhS(CH(2))(5)SPh produces the isomorphous 1D-compound [{Cu(μ(2)-Br)(2)Cu}{μ-PhS(CH(2))(5)SPh}(2)](n) (6). Strongly luminescent [Cu(4)I(4){μ-p-TolS(CH(2))(5)STol-p}(2)](n) (7) is obtained after mixing 1,5-bis(p-tolylthio)pentane with CuI in a 1:2 ratio, and the 2D-polymer [{Cu(μ(2)-I)(2)Cu}(2){μ-p-TolS(CH(2))(5)STol-p}(2)](n) (8) results from reaction in a 1:1 metal-to-ligand ratio. Under the same reaction conditions, 1D-polymeric [{Cu(μ(2)-Br)(2)Cu}{μ-p-TolS(CH(2))(5)STol-p}(2)](n) (9) is formed using CuBr. This study reveals that the structure of the self-assembly process between CuX and ArS(CH(2))(m)SAr ligands is hard to predict. The solid-state luminescence spectra at 298 and 77 K of 2 and 4 exhibit very strong emissions around 535 and 560 nm, respectively, whereas those for 1 and 5 display weaker ones at about 450 nm. The emission lifetimes are longer for the longer wavelength emissions (>1.0 μs arising from the cubane species) and shorter for the shorter wavelength ones (<1.4 μs arising from the rhomboid units). The Br-containing species are found to be weakly fluorescent.

Coordination RC6H4S(CH2)8SC6H4R/(CuI)n Polymers (R (n) = H (4); Me (8)): An Innocent Methyl Group that Makes the Difference

“…[4a,c] However, 2D [{Cu(μ 2 ‐I) 2 Cu}{μ‐PhS(CH 2 ) 3 SPh} 2 ] n and [Cu 4 I 4 {μ‐PhS(CH 2 ) 3 SPh} 2 ] n networks were formed by varying the CuI‐to‐PhS(CH 2 ) 3 SPh ratio. [7a] A double‐interpenetrated 2D network [{Cu(μ 2 ‐I) 2 Cu}{μ‐PhS(CH 2 ) 4 SPh} 2 ] n resulted from treatment of CuI with PhS(CH 2 ) 4 SPh. [7b] Mixing CuI and the dithioether in a 2:1 ratio resulted in the formation of [Cu 4 I 4 {μ‐PhS(CH 2 ) 5 SPh} 2 ] n , in which cubane‐like Cu 4 (μ 3 ‐I) 4 clusters are linked by bridging PhS(CH 2 ) 5 Ph ligands affording a 1D necklace CP similar to that of [Cu 4 I 4 {μ 2 ‐PhSCH 2 SPh} 2 ] n .…”

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].…”

Crystal structure of di-μ-iodido-bis[bis(acetonitrile-κN)copper(I)]

“…The title molecule is the active species used for the synthesis of luminescent compounds with (CuI) n moieties, prepared by treatment with sulfur ligands. For more details of syntheses and properties of these compounds, see: Knorr et al (2012Knorr et al ( , 2014Knorr et al ( , 2015. The N-Cu-N angle of 100.47 (10) in the title compound is comparable with that found in the pyridinecoordinated CuI dimer (Dyason et al, 1984).…”