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.
A unique pentanuclear cluster within a zeolite-type polymer ([Cu5(μ4-Br)(μ3-Br)2(μ2-Br)2](μ2-MeSPr)3)n (1; void space >81%) and a luminescent 1D ([Cu(μ3-I)]4(MeSPr)3)n polymer, 2, are formed when MeSPr reacts with CuBr and CuI.
Red (no styryl), green (monostyryl), and blue (distyryl) BODIPY-gallium(III) (BODIPY = boron-dipyrromethene) corrole dyads have been prepared in high yields using click chemistry, and their photophysical properties are reported. An original and efficient control of the direction of the singlet energy transfers is reported, going either from BODIPY to the gallium-corrole units or from gallium-corroles to BODIPY, depending upon the nature of the substitution on BODIPY. In one case (green), both directions are possible. The mechanism for the energy transfers is interpreted by means of through-space Förster resonance energy transfer (FRET).
The reaction of CuI with the highly flexible dithioether ligand p-TolS(CH2)8STol-p affords both in MeCN or in EtCN the 2D coordination polymers [Cu8I8{p-TolS(CH2)8STol-p}3(solvent)2]n (1·MeCN and 1·EtCN) containing octanuclear Cu8I8 clusters as connection nodes. In contrast, treatment of CuI with p-tBuC6H4S(CH2)8SC6H4But-p in EtCN solution leads to the formation of the luminescent 1D CP [Cu4I4{tBuC6H4S(CH2)8SC6H4-tBu}2(EtCN)2]n (2·EtCN) incorporating Cu4(μ3-I)4 clusters of the closed cubane type as secondary building units (SBUs). The 2D coordination polymers 1·MeCN and 1·EtCN demonstrate the ability to lose their solvent crystallisation molecules under vacuum and readsorb the same or a new one using vapor as monitored by powder X-ray diffraction, thermogravimetric, IR, chromaticity, emission spectra and emission lifetime measurements. Conversely, the 1D material 2·EtCN does not readsorb EtCN, likely due to the collapse of the macrocycles formed by the metal cluster nodes and flexible long-chained ArSC8SAr ligands but absorbs a smaller substrate such as CO2.
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