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Title: Structure, dynamics, and photophysics in the copper (I) iodide-tetrahyrothiophene system

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Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC); Materials Science of Actinides (MSA)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
DOE Contract Number:
Resource Type:
Journal Article
Resource Relation:
Journal Name: Crystal Growth and Design; Journal Volume: 14; Related Information: MSA partners with University of Notre Dame (lead); University of California, Davis; Florida State University; George Washington University; University of Michigan; University of Minnesota; Oak Ridge National Laboratory; Oregon state University; Rensselaer Polytechnic Institute; Savannah River National Laboratory
Country of Publication:
United States
nuclear (including radiation effects), materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly)

Citation Formats

Henline, Kylie, Wang, Charles, Pike, R.D., Ahern, J.C., Sousa, B., Patterson, H.H., Kerr, A. T., and Cahill, Christopher L.. Structure, dynamics, and photophysics in the copper (I) iodide-tetrahyrothiophene system. United States: N. p., 2014. Web. doi:10.1021/cg500005p.
Henline, Kylie, Wang, Charles, Pike, R.D., Ahern, J.C., Sousa, B., Patterson, H.H., Kerr, A. T., & Cahill, Christopher L.. Structure, dynamics, and photophysics in the copper (I) iodide-tetrahyrothiophene system. United States. doi:10.1021/cg500005p.
Henline, Kylie, Wang, Charles, Pike, R.D., Ahern, J.C., Sousa, B., Patterson, H.H., Kerr, A. T., and Cahill, Christopher L.. Wed . "Structure, dynamics, and photophysics in the copper (I) iodide-tetrahyrothiophene system". United States. doi:10.1021/cg500005p.
title = {Structure, dynamics, and photophysics in the copper (I) iodide-tetrahyrothiophene system},
author = {Henline, Kylie and Wang, Charles and Pike, R.D. and Ahern, J.C. and Sousa, B. and Patterson, H.H. and Kerr, A. T. and Cahill, Christopher L.},
abstractNote = {},
doi = {10.1021/cg500005p},
journal = {Crystal Growth and Design},
number = ,
volume = 14,
place = {United States},
year = {Wed Mar 05 00:00:00 EST 2014},
month = {Wed Mar 05 00:00:00 EST 2014}
  • 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 μ2-THT ligands. Dull yellow luminescent (CuI)10(THT)7(MeCN) (2) contains {[Cu4I4(THT)](μ2-THT)2(Cu2I2)(μ2-THT)2[Cu4I4(NCMe)]} “rungs” linked into 1-D ladders by pairs of μ2-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 °C, but it undergoes endothermic transformation to monoclinic 3a at 38 °C. Compound 3a transforms to a triclinic phase (3a') that retains orange emission atmore » -60 °C. Nonemissive (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 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.« less
  • The authors have determined the crystal structure of the compound ((CuL)I)I x 2.5H2O where L is C16H32N4, 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclo-tetradeca-4,11-diene (Syntex P21 automatic diffractometer, Mo K radiation, 3700 measured I/sub hk ell/ of which 2600 greater than or equal to 2sigma/sub I/, Theta/2 Theta scanning, 3 less than or equal to 2 theta less than or equal to 47). The metric of the unit cell is: a = 7.702(2), b = 20.755(8), c = 17.295(6) A, US = 115.09(2), V = 2504(1) AT, d/sub calc/ = 1.71 g/cmT, Z = 4, space group P21/C. The structure is of the island type. Themore » nearest environment of the Cu atom consists of four N macrocyclic ligands with mean Cu-N distance 1.99 A, forming an almost plane square. The two independent I anions are also crystallochemically different: they make up the coordination of the Cu atom to pyramidal (coordination number 4 + 1, Cu-I, 3.031 A), forming a cation of the composition ((CuL)I) . The second I is an anion and together with H2O molecules lies between these complex cations. The H2O molecules are joined by hydrogen bonds.« less
  • The structure of the polymeric rhodanine compound Cul(HN-CO-CH/sub 2/-S-CS)/sub 2/, C/sub 6/H/sub 6/CuIN/sub 2/O/sub 2/S/sub 4/, was determined by X-rays. M /SUB r/ = 456.8, monoclinic, space group P2/sub 1//c, a = 4.1947(7), b = 17.6999(12), C = 17.1048(8) A, ..beta.. = 96.15(1)/sup 0/, V /SUB c/ = 1262.6 A/sup 3/, Z = 4, D /SUB c/ = 2.40Mg m/sup -3/, Cu K..cap alpha.. radiation (graphite crystal monochromator, lambda = 1.54056 A), K..cap alpha..) = 278.9 cm/sup -1/, F(000) = 872, T = 290 K. Final conventional R - factor = 0.029, and R /SUB w/ = 0.044 formore » 2384 unique reflections and 153 variables. The structure was solved using Patterson methods and DIRDIF, and refined by full-matrix least-squares methods. The compound forms zigzag chains (..-Cu-I-Cu-..) along a. The copper atom is in trigonal pyramidal coordination, with two sulfur atoms of the thiocarbonyl group and two bridging iodine atoms. The copper-sulfur distances are 2.278(1) and 2.299(1) A, and the copper-iodine distances are 2.657(1) and 2.814(1) A.« less
  • The molecular structure and dynamics of the photoexcited metal-to-ligand-charge-transfer (MLCT) state of [Cu{sup I}(dmp){sub 2}]{sup +}, where dmp is 2,9-dimethyl-1,10-phenanthroline, in acetonitrile have been investigated by time-domain pump-probe X-ray absorption spectroscopy, femtosecond optical transient spectroscopy, and density functional theory (DFT). The time resolution for the excited state structural determination was 100 ps, provided by single X-ray pulses from a third generation synchrotron source. The copper ion in the thermally equilibrated MLCT state has the same oxidation state as the corresponding copper(II) complex in the ground state and was found to be penta-coordinate with an average nearest neighbor Cu-N distance 0.04more » {angstrom} shorter than that of the ground state [Cu{sup I}(dmp){sub 2}]{sup +}. The results confirm the previously proposed 'exciplex' structure of the MLCT state in Lewis basic solvents. The evolution from the photoexcited Franck-Condon MLCT state to the thermally equilibrated MLCT state was followed by femtosecond optical transient spectroscopy, revealing three time constants of 500--700 fs, 10--20 ps, and 1.6--1.7 ns, likely related to the kinetics for the formation of the triplet MLCT state, structural relaxation, and the MLCT excited-state decay to the ground state, respectively. DFT calculations are used to interpret the spectral shift on structural relaxation and to predict the geometries of the ground state, the tetracoordinate excited state, and the exciplex. The DFT calculations also indicate that the amount of charge transferred from copper to the dmp ligand upon photoexcitation is similar to the charge difference at the copper center between the ground-state copper(I) and copper(II) complexes.« less