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Metal-Cation-Directed Assembly of Two M–I (M = Cu, Ag) Clusters: Structures, Thermal Behaviors, Theoretical Studies, and Luminescence Properties

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Abstract

Two new M–I (M = Cu, Ag) clusters, {[Ce(DMF)8][Cu8I11]·C2H5OH} n (1) (DMF = dimethylfomamide) and {[Co(DMF)6]4[Ag7I11]2} (2), were synthesized with the direction of solvent-associated metal cations ([Ce(DMF)8]3+ in 1 and [Co(DMF)6]2+ for 2). Clusters 1 and 2 have been well-characterized by elemental analysis, infrared spectroscopy, ultraviolet/visible spectroscopies, single-crystal X-ray diffraction and thermogravimetric analysis. 1 contains the eight-coordinated cations [Ce(DMF)8]3+ and 1D polymeric anionic chain {[Cu8I11]3−} n , which is constructed from [Cu8I11]3− clusters connected with each other through µ 3-I bridges and exhibits an interesting wavy chain structure. Cluster 2 consists of the six-coordinated cations [Co(DMF)6]2+ and the dimeric anionic cluster {[Ag7I11]2}8−, which is fabricated by a pair of heptanuclear butterfly-like clusters connected by two Ag–I bridges. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations at the B3LYP/LanL2DZ*+6-31G* level were performed on clusters 1 and 2 to rationalize their experimental absorption spectra. Solid-state luminescence properties of clusters 1 and 2 have also been investigated at room temperature.

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Acknowledgments

Financial support from the National Natural Science Foundation of China (Grant Nos.: 50925207, 51172100, and 51432006), the Ministry of Science and Technology of China for the International Science Linkages Program (Grant No.: 2011DFG52970), the Ministry of Education of China for the Changjiang Innovation Research Team (Grant No.: IRT13R24), the Ministry of Education and the State Administration of Foreign Experts Affairs for the 111 Project (Grant No.: B13025), and 100 Talents Program of CAS are gratefully acknowledged.

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Authors and Affiliations

  1. Institute of Molecular Engineering and Advanced Materials, School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing, 210094, People’s Republic of China

    Wenjiang Huang, Hongyang Wei & Chi Zhang

  2. China-Australia Joint Research Center for Functional Molecular Materials, Scientific Research Academy, Jiangsu University, Zhenjiang, 212013, People’s Republic of China

    Longhua Li & Jun Qian

  3. China-Australia Joint Research Center for Functional Molecular Materials, School of Chemical and Material Engineering, Jiangnan University, Wuxi, 214122, People’s Republic of China

    Chi Zhang

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  1. Wenjiang Huang
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Correspondence to Jun Qian or Chi Zhang.

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Huang, W., Wei, H., Li, L. et al. Metal-Cation-Directed Assembly of Two M–I (M = Cu, Ag) Clusters: Structures, Thermal Behaviors, Theoretical Studies, and Luminescence Properties. J Clust Sci 27, 1463–1474 (2016). https://doi.org/10.1007/s10876-016-1012-0

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