Journal
CRYSTAL GROWTH & DESIGN
Volume 9, Issue 11, Pages 4963-4968Publisher
AMER CHEMICAL SOC
DOI: 10.1021/cg9007608
Keywords
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Funding
- National Natural Science Foundation of China [20525101, 20871088]
- State Key Laboratory of Organometallic Chemistry of Shanghai Institute of Organic Chemistry [08-25]
- Qin-Lan Project
- Suzhou University
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Solvothermal reactions of CuI with 4,4'-dipyridyl disulfide (dpds) and oxalic acid in toluene and acetonitrile at three different time periods gave rise to three Cu/I/S-based coordination polymers, [Cu-6(mu-4-SpyH)(4)I-6](n) (1), {[Cu-2(mu-I)(mu-4-SpyH)(3)]I}(n) (2), and [Cu-5(mu-4-SpyH)(7)(mu-I)I-4](n) (3). The preparation of 1-3 was involved in the in situ formation of the zwitterionic pyridium-4-thiolate (4-SpyH) molecule from the S-S cleavage of the dpds ligand. These compounds were characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), X-ray powder diffraction (XRPD), and single crystal X-ray diffraction. Compound 1 contains an adamantine-type [CU6S4] core that links the neighboring ones via double iodide bridges to form a three-dimensional (3D) diamond-like net. Compound 2 has a one-dimensional (1D) cationic {[Cu-2(mu-I)(mu-4-SpyH)(3)](n)}(n+) polymeric chain with disordered iodides embedded between chains. Compound 3 contains the [Cu-5(mu-I)I-4(mu-4-SpyH)(7)] species that is interconnected with its neighboring ones through two mu-4-SpyH ligands to form a 1D neutral chain. The formation of 1-3 provided an interesting example that different coordination polymers could be produced from the same components under solvothermal conditions at different time periods. In addition, optical absorption and electric conductivity experiments revealed that 1-3 exhibited good semiconducting performances.
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