Reactivity of CuI and CuBr toward Dialkyl Sulfides RSR: From Discrete Molecular Cu₄I₄S₄ and Cu₈I₈S₆ Clusters to Luminescent Copper(I) Coordination Polymers

Abstract

The 1D coordination polymer (CP) [(Me2S)3{Cu2(μ-I)2}]n (1) is formed when CuI reacts with SMe2 in n-heptane, whereas in acetonitrile (MeCN), the reaction forms exclusively the 2D CP [(Me2S)3{Cu4(μ-I)4}]n (2) containing "flower-basket" Cu4I4 units. The reaction product of CuI with MeSEt is also solvent-dependent, where the 1D polymer [(MeSEt)2{Cu4(μ3-I)2(μ2-I)2}(MeCN)2]n (3) containing "stepped-cubane" Cu4I4 units is isolated in MeCN. In contrast, the reaction in n-heptane affords the 1D CP [(MeSEt)3{Cu4(μ3-I)4}]n (4) containing "closed-cubane" Cu4I4 clusters. The reaction of MeSPr with CuI provides the structurally related 1D CP [(MeSPr)3{Cu4(μ3-I)4}]n (5), for which the X-ray structure has been determined at 115, 155, 195, 235, and 275 K, addressing the evolution of the metric parameters. Similarly to 4 and the previously reported CP [(Et2S)3{Cu4(μ3-I)4}]n (Inorg. Chem. 2010, 49, 5834), the 1D chain is built upon closed cubanes Cu4(μ3-I)4 as secondary building units (SBUs) interconnected via μ-MeSPr ligands. The 0D tetranuclear clusters [(L)4{Cu4(μ3-I)4}] [L = EtSPr (6), Pr2S (7)] respectively result from the reaction of CuI with EtSPr and n-Pr2S. With i-Pr2S, the octanuclear cluster [(i-Pr2S)6{Cu8(μ3-I)3}(μ4-I)2}] (8) is formed. An X-ray study has also been performed at five different temperatures for the 2D polymer [(Cu3Br3)(MeSEt)3]n (9) formed from the reaction between CuBr and MeSEt in heptane. The unprecedented framework of 9 consists of layers with alternating Cu(μ2-Br)2Cu rhomboids, which are connected through two μ-MeSEt ligands to tetranuclear open-cubane Cu4Br4 SBUs. MeSPr forms with CuBr in heptane the 1D CP [(Cu3Br3)(MeSPr)3]n (10), which is converted to a 2D metal-organic framework [(Cu5Br5)(μ2-MeSPr)3]n (11) incorporating pentanuclear [(Cu5(μ4-Br)(μ2-Br)] SBUs when recrystallized in MeCN. The thermal stability and photophysical properties of these materials are also reported.

Strong luminescent copper(i) halide coordination polymers and dinuclear complexes with thioacetamide and N,N′-donor ligands

“…[38][39][40] However, design and structure prediction still remains a challenge. Despite the fact that there are some examples of CuIJI) halide coordination polymers based on ligands which contain at the same time hard N and soft S donor atoms, 5,[41][42][43][44][45] or organosulfur ligands and acetonitrile, 46,47 to the best of our knowledge, the combination of organosulfur and N-heteroaromatic ligands to obtain CuIJI) halide coordination polymers still remains unexplored. Introduction of N,N′ditopic ligands, such as 4,4′-bipyridine and pyrazine, to the CuX-thioacetamide system might lead to new compounds with intriguing structures and improved electrical and luminescence properties.…”

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).…”

“…dimethyl sulfide). After stirring, the solution was stored in a refridgerator over night, followed by keeping it in a freezer (Knorr et al, 2015). In addition to the crystallized CuI compounds, the title compound could be isolated in traces.…”

Tripyridine‐Derivative‐Derived Semiconducting Iodo‐Argentate/Cuprate Hybrids with Excellent Visible‐Light‐Induced Photocatalytic Performance

“…The halide ions (Cl − , Br − , I − ) can serve as bridges from terminal to μ 2 ‐ and up to μ 8 ‐bridging. The combination of halide ions and different metal atoms, directed by various organic templates, has formed numerous captivating structures . Recently, Guo et al.…”

“…The combinationo fh alide ions and differentm etal atoms, directed by variouso rganic templates, has formedn umerous captivating structures. [38][39][40][41][42][43][44][45][46][47] Recently, Guo et al prepared as eries of chlorobismuthates and iodoplu-bates hybridsw ith excellent electronic conducting and luminescencep roperties. [11][12][48][49][50] Leia nd Yuee tal.…”