| Full text | |
| Author(s): |
Surbella, III, Robert G.
;
Ducati, Lucas C.
[1]
;
Autschbach, Jochen
[2]
;
Deifel, Nicholas P.
[3]
;
Cahill, Christopher L.
[4]
Total Authors: 5
|
| Affiliation: | [1] Univ Sao Paulo, Inst Chem, Dept Fundamental Chem, Ave Prof Lineu Prestes 748, BR-05508000 Sao Paulo, SP - Brazil
[2] SUNY Buffalo, Dept Chem, 312 Nat Sci Complex, Buffalo, NY 14260 - USA
[3] Hampden Sydney Coll, Dept Chem, Hampden Sydney, VA 23943 - USA
[4] Surbella, Robert G., III, George Washington Univ, Dept Chem, 800 22nd St NW, Washington, DC 20052 - USA
Total Affiliations: 4
|
| Document type: | Journal article |
| Source: | Inorganic Chemistry; v. 57, n. 5, p. 2455-2471, MAR 5 2018. |
| Web of Science Citations: | 10 |
| Abstract | |
The synthesis and structural characterization of seven new {[}UO2(NCS)(5)](3-)- and {[}UO2(NCS)(4)Cl](3-)-containing materials charge balanced by 4-phenylpyridinium or 4,4'-bipyridinium cations are reported. Assembly of these materials occurs via a diverse set of noncovalent interactions, with the most prevalent involving the terminal sulfur atoms, which can both accept hydrogen bonds and/or form S center dot center dot center dot S and S center dot center dot center dot O-yl interactions. The electrostatic potential of the {[}UO2(NCS)(5)](3-) and {[}UO2(NCS)(4)Cl](3-) anions was calculated and mapped on the 0.001 au isodensity surface to rationalize the observed assembly modes and to provide an electrostatic basis to elucidate the role of the S atoms as both donors and acceptors of noncovalent interactions. Compounds 1-7 display a range of colors (red to yellow) as well as pronounced thermochromism. A computational treatment (time-dependent density functional theory, TDDFT) of the absorbance properties supports the temperature dependence on the ratio of inter- to intramolecular ligand to metal charge transfer (LMCT) bands as obtained from UV-vis diffuse reflectance analysis. Finally, the luminescence profiles of these materials feature additional peaks atypical for most uranyl-containing materials, and a combined spectroscopic (Raman, IR, and fluorescence) and computational (harmonic frequency calculations) effort assigns these as originating from vibronic coupling between the nu(1) U=O symmetric stretch and bending modes of the isothiocyanate ligands. (AU) | |
| FAPESP's process: | 14/21930-9 - Study of the solvent effect on the spin spin coupling constant 1JPt-Tl in heavy metal complexes by ab initio molecular dynamics |
| Grantee: | Lucas Colucci Ducati |
| Support Opportunities: | Scholarships abroad - Research |