Completely Unexpected Coordination Selectivity of Copper Iodide for Thioether Over Ethynyl

Abstract

The reactivity of the tetradentate ligand bis(p-thiomethylphenylacetylene) (MeSC 6 H 4 C≡C-C≡CC 6 H 4 SMe; L2) towards the CuI salt is compared to that for the known organometallic analogue trans-bis(p-thiomethylethynylbenzene)bis(trimethylphosphine)platinum(II) (trans-Pt(PMe 3) 2 (C≡CC 6 H 4 SMe) 2 ; L1). While L1 with CuI form a highly luminescent porous 2D coordination polymer (CP) of general formula ([Cu 4 I 4 ]L1 • EtCN) n (CP1; Juvenal et al. in Inorg Chem 55:11096-11109, 2016) exhibiting both Cu(η 2-C≡C) and Cu-S bonds, L2 reacts with CuI to produce a luminescent non-porous 2D CP exhibiting the general formula ([Cu 4 I 4 ]{L2} 3) n , CP2, which does not use the highly expected Cu(η 2-C≡C) linkage, relying strictly upon Cu-S coordination. An examination of the X-ray structures for both L2 and CP2 indicates that CP2 network is built upon an expansion of the L2 lattice (plane sliding and slight L2-L2 distance separation) resembling to a sort of template effect. CP2 has been characterized by TGA, UV-Vis, emission spectroscopy, and photophysics, which are accompanied by DFT and TDDFT computations.

2,2′-Ethylenebis(1,3-dithiane) as a polydentate μ2-, μ4- and μ5-assembling ligand for the construction of sulphur-rich Cu(i), Hg(ii) and heterometallic Cu(i)/Hg(ii) coordination polymers featuring uncommon network architectures

“…Several other compounds such as CP8, CP9, D1 and M1 also bear such potential S-donor sites allowing to use them as so-called metalloligand, a concept which has been successfully probed in organophosphorus coordination chemistry using [ML n (κ 1dppm)] featuring a dangling bis(diphenylphosphino)methane ligand to assemble heterometallic scaffolds. [73][74][75] For other strategies to assemble heterobimetallic thioether-based materials see: 76,77 This feature opens the possibility for forthcoming work to construct systematically heterometallic assemblies by the coordination of other ML n fragments or MX n salt, which may in turn serve as promising precursors after controlled thermolysis or chemical post-functionalisation for heterometallic phases and other materials. 78…”

“…Several other compounds such as CP8 , CP9 , D1 and M1 also bear such potential S -donor sites allowing to use them as so-called metalloligand, a concept which has been successfully probed in organophosphorus coordination chemistry using [ML n (κ 1 -dppm)] featuring a dangling bis(diphenylphosphino)methane ligand to assemble heterometallic scaffolds. 73–75 For other strategies to assemble heterobimetallic thioether-based materials see: 76,77…”

Polymeric CuX coordination compounds assembled from acetylenic thioether ligands RSCH2CCCH2R (R = C6H11, t-Bu): effect of the RS-group, halide and stoichiometry on the network architecture and the luminescence properties

“…[19][20][21] Other examples are the π-conjugated ligand 9,10-bis{ [3,4bis(methylthio)phenyl]ethynyl}anthracene, which interacts with CuCN to form a luminescent 2D network, 22 the dinuclear species [{Cu(μ 2 -Br) 2 Cu}(PhSCH 2 CCH) 4 ] 23 and the luminescent 2D CP formed upon coordination of the bis(pthiomethylphenylacetylene) ligand with CuI with noncoordinating alkynyl groups. 24 Our group recently investigated the parameters that influence the resulting polymer structure, cluster shape and photophysical data using the rigid ligands p-TolSCH 2 CCCH 2 Sp-Tol and PhSCH 2 CCCH 2 SPh. 25,26 The former ligand led to the formation of a 2D network [{Cu 4 (μ 3 -I) 4 } (μ-p-MeC 6 H 4 SCH 2 CCCH 2 Sp-MeC 6 H 4 ) 2 ] n with closed cubanetype clusters as SBUs, whereas the latter acetylenic dithioether provided a 3D network [(Cu 6 I 6 )(μ-PhSCH 2 CCCH 2 SPh) 3 ] n using the hexagonal prism cluster as connection nodes.…”

“…19–21 Other examples are the π-conjugated ligand 9,10-bis{[3,4-bis(methylthio)phenyl]ethynyl}anthracene, which interacts with CuCN to form a luminescent 2D network, 22 the dinuclear species [{Cu(μ 2 -Br) 2 Cu}(PhSCH 2 CCH) 4 ] 23 and the luminescent 2D CP formed upon coordination of the bis( p -thiomethylphenylacetylene) ligand with CuI with non-coordinating alkynyl groups. 24…”