Structure, Dynamics, and Photophysics in the Copper(I) Iodide鈥揟etrahydrothiophene System
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- 作者：Kylie M. Henline ; Charles Wang ; Robert D. Pike ; John C. Ahern ; Bryer Sousa ; Howard H. Patterson ; Andrew T. Kerr ; Christopher L. Cahill
- 刊名：Crystal Growth & Design
- 出版年：2014
- 出版时间：March 5, 2014
- 年：2014
- 卷：14
- 期：3
- 页码：1449-1458
- 全文大小：501K
- 年卷期：v.14,no.3(March 5, 2014)
- ISSN：1528-7505
文摘
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 (1) consists of Cu4I4 cubane units knit into a 3-D network by 渭2-THT ligands. Dull yellow luminescent (CuI)10(THT)7(MeCN) (2) contains {[Cu4I4(THT)](渭2-THT)2(Cu2I2)(渭2-THT)2[Cu4I4(NCMe)]} 鈥渞ungs鈥?linked into 1-D ladders by pairs of 渭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 掳C, but it undergoes endothermic transformation to monoclinic 3a at 38 掳C. Compound 3a transforms to a triclinic phase (3a鈥? that retains orange emission at 鈭?0 掳C. Nonemissive (CuI)3(THT)3路MeCN (4) is a 2-D sheet structure in which Cu3(THT)3 rings are linked in trigonal directions by rhomboid Cu2I2 dimer units. The previously reported (CuI)2(THT)4 (5) is a molecular dimer. Temperature and mixing ratio domains for the formation of the CuI鈥揟HT 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.