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Issue 40, 2012
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Synthesis, structure and band gap energy of covalently linked cluster-assembled materials

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Abstract

We have synthesized a series of cluster assembled materials in which the building blocks are As73− clusters linked by group 12 metals, Zn, Cd and Hg, to investigate the effect of covalent linkers on the band gap energy. The synthesized assemblies include zero dimensional assemblies of [Zn(As7)2]4−, [Cd(As7)2]4−, [Hg2(As7)2]4−, and [HgAsAs14]3− in which the clusters are separated by cryptated counterions, and assemblies in which [Zn(As7)2]4−, [Cd(As7)2]4− are linked by free alkali atoms into unusual three-dimensional structures. These covalently linked cluster-assembled materials have been characterized by elemental analysis, EDX and single-crystal X-ray diffraction. The crystal structure analysis revealed that in the case of Zn and Cd, the two As73− units are linked by the metal ion, while in the case of Hg, two As73− units are linked by either Hg–Hg or Hg–As dimers. Optical measurements indicate that the band gap energy ranges from 1.62 eV to 2.21 eV. A theoretical description based on cluster orbital theory is used to provide a microscopic understanding of the electronic character of the composite building blocks and the observed variations in the band gap energy.

Graphical abstract: Synthesis, structure and band gap energy of covalently linked cluster-assembled materials

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Publication details

The article was received on 14 Jun 2012, accepted on 26 Jul 2012 and first published on 30 Jul 2012


Article type: Paper
DOI: 10.1039/C2DT31286G
Citation: Dalton Trans., 2012,41, 12365-12377
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    Synthesis, structure and band gap energy of covalently linked cluster-assembled materials

    S. Mandal, A. C. Reber, M. Qian, R. Liu, H. M. Saavedra, S. Sen, P. S. Weiss, S. N. Khanna and A. Sen, Dalton Trans., 2012, 41, 12365
    DOI: 10.1039/C2DT31286G

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