title: 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.
authors.affiliation: †Institut UTINAM, UMR CNRS 6213, Université de Franche-Comté, 16 Route de Gray, 25030 Besançon, France.
authors.forename: Michael
authors.initials: M
authors.lastname: Knorr
authors.affiliation: ‡Département de Chimie, Université de Sherbrooke, 2500 Boulevard Université, Sherbrooke, Quebec J1K 2R1, Canada.
authors.forename: Antoine
authors.initials: A
authors.lastname: Bonnot
authors.affiliation: †Institut UTINAM, UMR CNRS 6213, Université de Franche-Comté, 16 Route de Gray, 25030 Besançon, France.|‡Département de Chimie, Université de Sherbrooke, 2500 Boulevard Université, Sherbrooke, Quebec J1K 2R1, Canada.
authors.forename: Antony
authors.initials: A
authors.lastname: Lapprand
authors.affiliation: †Institut UTINAM, UMR CNRS 6213, Université de Franche-Comté, 16 Route de Gray, 25030 Besançon, France.
authors.forename: Abderrahim
authors.initials: A
authors.lastname: Khatyr
authors.affiliation: §Anorganische Chemie, Technische Universität Dortmund, Otto-Hahn-Strasse 6, 44227 Dortmund, Germany.
authors.forename: Carsten
authors.initials: C
authors.lastname: Strohmann
authors.affiliation: ⊥Institut de Chimie Moléculaire, UMR CNRS 6302, Université de Bourgogne, 9 Avenue A. Savary, 21087 Dijon, France.
authors.forename: Marek M
authors.initials: MM
authors.lastname: Kubicki
authors.affiliation: ⊥Institut de Chimie Moléculaire, UMR CNRS 6302, Université de Bourgogne, 9 Avenue A. Savary, 21087 Dijon, France.
authors.forename: Yoann
authors.initials: Y
authors.lastname: Rousselin
authors.affiliation: ‡Département de Chimie, Université de Sherbrooke, 2500 Boulevard Université, Sherbrooke, Quebec J1K 2R1, Canada.
authors.forename: Pierre D
authors.initials: PD
authors.lastname: Harvey