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 Pol

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• 作者：Michael Knorr ; Abderrahim Khatyr ; Ahmed Dini Aleo ; Anass El Yaagoubi ; Carsten Strohmann ; Marek M. Kubicki ; Yoann Rousselin ; Shawkat M. Aly ; Daniel Fortin ; Antony Lapprand ; Pierre D. Harvey
• 刊名：Crystal Growth & Design
• 出版年：2014
• 出版时间：November 5, 2014
• 年：2014
• 卷：14
• 期：11
• 页码：5373-5387
• 全文大小：910K
• ISSN：1528-7505

文摘

Bis(phenylthio)methane (L1) reacts with CuI to yield the 1D-coordination polymer [{Cu₄(渭₃-I)₄}(渭-L1)₂]_n (1) bearing cubane Cu₄I₄ 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 C2/c to P2₁/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 [{Cu₄(渭₃-I)₄}(渭-Lx)₂]_n (x = 2, 3, or 4). Compounds 2 and 4 are isostructural with C2/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 [{Cu₄(渭₃-I)₄}(渭-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 [{Cu₄(渭₃-I)₄}(渭-L8)₂]_n (8). The 1D polymer [{Cu(渭₂-Br)₂Cu}(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路路路Cu distances, which are <2.8 脜 noted for the Cu₄(渭₃-I)₄ clusters in the 1D polymers 1鈥?b>8, the Cu路路路Cu contact within the Cu(渭₂-Br)₂Cu rhomboids of 9 [2.9194(8) 脜] is above the sum of the van der Waals radii of two Cu atoms. The structural arrangement of 1D polymer [{Cu(渭₂-Br)₂Cu}(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(渭₂-Br)₂Cu}(L5)₂]_n (12), the reaction of CuBr with L2 leads to the dinuclear complex [{Cu(渭₂-Br)₂Cu}(畏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(渭₂-Br)₂Cu}(MeCN)₂(畏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 Cu₄I₄ core (1鈥?b>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路路路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.