Journal
DALTON TRANSACTIONS
Volume 42, Issue 43, Pages 15475-15481Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c3dt51451j
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Funding
- NSF of China [90922035, 21003126, 91222204]
- National Key Technology RD Program [2012BAE06B08]
- Key Project from the CAS [KJCX2-EW-H03]
- NSF of Fujian Province [2010H0022]
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Two new inorganic supramolecular compounds, (Hg11P4)(GaCl4)(4) (1) and (Hg3AsS)(GaCl4) (2), have been prepared by the solid-state reactions. Their structures are characterized by mercury-containing cationic hosts and discrete (GaCl4)(-) guests, which is a derivative of a very strong Lewis acid. The three-dimensional cationic framework of 1, (Hg11P4)(4+), is marvellously extended by Hg-2(2+) and Hg-3(2+) groups as well as Hg2+ ions to form two large tunnels with different sizes each embedded with two columns of (GaCl4)(-) anions. Compound 2 features a layered structure with (GaCl4)(-) tetrahedra being intercalated between two-dimensional (Hg3AsS)(+) layers and it is the first mercury pnictidechalcohalide. It is found that the weak electrostatic forces between hosts and guests play a key role in the stabilization of the whole structures of 1 and 2, which is strikingly different from almost all the reported metal pnictidehalide and chalcohalide supramolecular compounds. Optical dielectric constants calculations show that both 1 and 2 possess strong dielectric anisotropy.
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