Multifunctional Copper(I) Coordination Polymers with Aromatic Mono- and Ditopic Thioamides

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry 58.5 (2019): 3290-3301, © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see: https://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.8b03364Direct reactions under ambient conditions between CuX (X = Br, I) and thiobenzamide (TBA) were carried out at different ratios, giving rise to the formation of a series of one-dimensional (1D) coordination polymers, (CPs) [CuI(TBA)] n (1), [Cu 3 I 3 (TBA) 2 ] n (4), and [CuBr(TBA)] n (5), as well as two molecular complexes, [CuI(TBA) 3 ] (2) and [Cu 2 I 2 (TBA) 4 ]·2MeCN (3). Recrystallization of 1 and 5 yielded a series of isostructural 1D CP solvated species, [CuI(TBA)·S] n ] n (1·S; S = tetrahydrofuran, acetone, methanol) and [CuBr(TBA)·S] n (5·S; S = tetrahydrofuran, acetone), respectively. Similar reactions between CuI and 1,4-dithiobenzamide (DTBA) allowed the isolation of a series of two-dimensional (2D) CPs [CuI(DTBA)·S] n (6·S; S = N,N-dimethylformamide, acetonitrile, methanol). Interestingly, 1·S and 5·S showed variable luminescence and electrical semiconductivity depending on the different solvents located in their structures. Thus, 1 and 5 could display potential application for sensing volatile organic vapors by virtue of the significant changes in their emission upon solvent exposure, even by the naked eye. Theoretical calculations have been used to rationalize these electronic propertiesMINECO (Grants MAT2016-77608-C3-1-P, MAT2016-75883-C2-1-P, and MAT2017-5089-C2-1-R; Ramon y Cajal, Grant RYC-2015-17730), Ministerio de Ciencia, Innovacion y Universidades (Grant CTQ2016-75816-C2-1-P), and European Union’s Horizon 2020 research and innovation programme (Grant 785219; Graphene Flagship−core2