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 �2-THT ligands. Yellow luminescent (CuI)10(THT)7(MeCN) (2  ) contains {[Cu4I4(THT)](�2-THT)2(Cu2I2)(�2-THT)2[Cu4I4(NCMe)]} 'rungs' linked into 1-D ladders by pairs of �2-THT ligands. Two molecular (CuI)4(THT)4 phases were found: orange luminescent 3a  and dull yellow luminescent 3b  . Triclinic 3b  is the more stable phase at 25 �C, but undergoes endothermic transformation to monoclinic 3a  at 38 �C. 3a  transforms to a triclinic phase (3a'  ) that retains orange emission at �60 �C. Non-emissive (CuI)3(THT)3�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-THT phases from MeCN are presented. Luminescence in 1  , 2  , 3a  , and 3b  is rationalized based on 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  .

Structure diversity and photoluminescence in CuI-tetrahydrothiophene complexes

248th National Meeting (2014)

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