期刊
CRYSTAL GROWTH & DESIGN
卷 14, 期 3, 页码 1449-1458出版社
AMER CHEMICAL SOC
DOI: 10.1021/cg500005p
关键词
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资金
- Virginia Space Grant Consortium
- Office of Basic Energy Sciences of the U.S. Department of Energy as part of the Materials Science of Actinides Energy Frontier Research Center [DE-SC0001089]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [0848109] Funding Source: National Science Foundation
Combination of CuI and tetrahydrothiophene (THT) in MeCN or neat THT produces various phases, depending upon experimental conditions. Green luminescent product (CuI)(4)(THT)(2) (I) consists of Cu4I4 cubane units knit into a 3-D network by mu(2)-THT ligands. Dull yellow luminescent (CuI)(10)(THT)(7)(MeCN) (2) contains {[Cu4I4(THT)](mu(2)-THT)(2) (CU2I2) (mu(2)-THT)(2)[Cu4I4(NCMe)]} rungs linked into 1-D ladders by pairs of mu(2)-THT ligands. Two molecular (CuI)(4)(THT)(4) phases were found: orange luminescent 3a and yellow luminescent 3b. Triclinic 3b is the more stable phase at 25 degrees C, but it undergoes endothermic transformation to monoclinic 3a at 38 C. Compound 3a transforms to a triclinic phase (3a') that retains orange emission at -60 degrees C. Nonemissive (CuI)(3)(THT)(3)center dot MeCN (4) is a 2-D sheet structure in which Cu-3(THT)(3) rings are linked in trigonal directions by rhomboid Cu2I2 dimer units. The previously reported (CuI)(2)(THT)(4) (S) is a molecular dimer. Temperature and mixing ratio domains for the formation of the CuI-THT phases from MeCN are presented. Luminescence in 1, 2, 3a, and 3b is rationalized on the basis of varying degrees of halide-to-metal charge transfer (XMCT) and metal-centered (MC) behavior. Low-temperature spectra reveal reversible changes, including modest red shifts for 1 and 2, and splitting into two excitation/emission band pairs for 3a and 3b.
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