Copper(I) Halides (X = Br, I) Coordinated to Bis(arylthio)methane Ligands: Aryl Substitution and Halide Effects on the Dimensionality, Cluster Size, and Luminescence Properties of the Coordination Polymers

Bis(phenylthio)methane ( L1 ) reacts with CuI to yield the 1D-coordination polymer [{Cu 4 (μ 3 -I) 4 }(μ- L1 ) 2 ] n ( 1 ) bearing cubane Cu 4 I 4 clusters as connecting nodes. The crystal structures at 115, 155, 195, and 235 K provided evidence for a phase transition changing from the monoclinic space group C 2/ c to P 2 1 / c . The self-assembly process of CuI with bis( p -tolylthio)methane ( L2 ), bis(4-methoxyphenylthio)methane ( L3 ), and bis(4-bromo-phenylthio)methane ( L4 ) affords the 1D-coordination polymers [{Cu 4 (μ 3 -I) 4 }(μ- L x ) 2 ] n ( x = 2, 3, or 4). Compounds 2 and 4 are isostructural with C 2/ c low temperature polymorph of 1, whereas the inversion centers and 2-fold axes are lost in 3 (space group Cc ). The use of bis( m -tolylthio)methane ( L5 ) has no impact on the composition and overall topology of the resulting 1D ribbon of [{Cu 4 (μ 3 -I) 4 }(μ- L5 ) 2 ] n ( 5 ). Even the coordination of the sterically crowded dithioether bis(5- tert -butyl-2-methylphenylthio)methane ( L8 ) does not alter the network topology generating the 1D polymer [{Cu 4 (μ 3 -I) 4 }(μ- L8 ) 2 ] n ( 8 ). The 1D polymer [{Cu(μ 2 -Br) 2 Cu}( L1 ) 2 ] ( 9 ) results from the coordination of L1 with CuBr in a 1:1 metal-to-ligand ratio. In contrast to the mean Cu···Cu distances, which are <2.8 Å noted for the Cu 4 (μ 3 -I) 4 clusters in the 1D polymers 1 – 8, the Cu···Cu contact within the Cu(μ 2 -Br) 2 Cu rhomboids of 9 [2.9194(8) Å] is above the sum of the van der Waals radii of two Cu atoms. The structural arrangement of 1D polymer [{Cu(μ 2 -Br) 2 Cu}( L3 ) 2 ] n ( 11 ) is quite similar to that of 9 . While the reaction of CuBr with L5 results in a similar 1D polymer [{Cu(μ 2 -Br) 2 Cu}( L5 ) 2 ] n ( 12 ), the reaction of CuBr with L2 leads to the dinuclear complex [{Cu(μ 2 -Br) 2 Cu}(η 1 - L2 ) 4 ] ( 10 ) ligated by four pendent bis( p -tolylthio)methane ligands. The ligation of bis( o -tolylthio)methane, L6, on CuBr also yields a discrete complex [{Cu(μ 2 -Br) 2 Cu}(MeCN) 2 (η 1 - L6 ) 2 ] ( 13 ) bearing MeCN and dangling dithioether ligands. A strong luminescence is detected for all CuI polymers, all exhibiting emission lifetimes in the microsecond time scale (i.e., phosphorescence). The polymers containing the Cu 4 I 4 core ( 1 – 8 ) exhibit the typically observed low-energy band and sometimes a weaker high-energy band. The nature of the low-energy band was proposed based on literature DFT and TDDFT computations and is predicted to be a mixture of cluster-centered (CC*) and metal/halide-to-ligand charger transfer (M/XLCT). An approximate relationship between the Cu···Cu distance and the emission maxima corroborates the CC* contribution to the nature of the excited states. The emission of the rhomboid-containing materials is assigned to M/XLCT based on literature works on similar motifs.

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