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Two other Cu<jats:sup>III<\/jats:sup> complexes were obtained by replacement of the alkali metal cations with tetrabutylammonium (TBA<jats:sup>+<\/jats:sup>), namely, TBA[Cu<jats:sup>III<\/jats:sup>(pds)<jats:sub>2<\/jats:sub>] (<jats:bold>3<\/jats:bold>), and TBA[Cu<jats:sup>III<\/jats:sup>(pdt)<jats:sub>2<\/jats:sub>] (<jats:bold>5<\/jats:bold>). All complexes were characterized by <jats:sup>1<\/jats:sup>H and <jats:sup>13<\/jats:sup>C NMR and IR spectroscopy, electronic absorption, elemental analysis, cyclic voltammetry (CV), and X\u2010ray crystallography. Electrical conductivity measurements on single crystals show that these salts exhibit insulating behavior. The crystal structure of these species revealed a lateral coordination capability of the N atoms of the pyrazine ring of both pds and pdt ligands towards the alkali metal ions, which leads to the build up of a net of coordinative bonds, hydrogen bonds, and contacts that result in the final 3D structure. Two parameters control the crystal engineering of the final 3D structures: the nature of the alkali metal countercation and the nature of the chalcogen atom (Se\/S), which allow fine\u2010tuning of complex 3D crystal lattice. Density functional calculations were performed on the [Cu(pds)<jats:sub>2<\/jats:sub>] and [Cu(pdt)<jats:sub>2<\/jats:sub>] systems to investigate the electronic structure of the complexes and understand their electronic and electrochemical behavior by studying the frontier molecular orbitals. This study also reveals whether the redox processes take place on the ligands or on the metal center, a question under continuous discussion in the literature.<\/jats:p>","DOI":"10.1002\/chem.200305422","type":"journal-article","created":{"date-parts":[[2004,3,25]],"date-time":"2004-03-25T13:59:58Z","timestamp":1080223198000},"page":"1691-1704","source":"Crossref","is-referenced-by-count":70,"title":["Novel Cu<sup>III<\/sup> Bis\u20101,2\u2010dichalcogenene Complexes with Tunable 3D Framework through Alkaline Cation Coordination: A Structural and Theoretical Study"],"prefix":"10.1002","volume":"10","author":[{"given":"Xavi","family":"Ribas","sequence":"first","affiliation":[]},{"given":"Jo\u00e3o C.","family":"Dias","sequence":"additional","affiliation":[]},{"given":"Jorge","family":"Morgado","sequence":"additional","affiliation":[]},{"given":"Klaus","family":"Wurst","sequence":"additional","affiliation":[]},{"given":"Elies","family":"Molins","sequence":"additional","affiliation":[]},{"given":"Eliseo","family":"Ruiz","sequence":"additional","affiliation":[]},{"given":"Manuel","family":"Almeida","sequence":"additional","affiliation":[]},{"given":"Jaume","family":"Veciana","sequence":"additional","affiliation":[]},{"given":"Concepci\u00f3","family":"Rovira","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2004,3,24]]},"reference":[{"unstructured":"\u00a0","key":"e_1_2_7_1_2"},{"doi-asserted-by":"publisher","key":"e_1_2_7_2_2","DOI":"10.1039\/C39810000067"},{"doi-asserted-by":"publisher","key":"e_1_2_7_3_2","DOI":"10.1016\/0379-6779(87)90482-6"},{"unstructured":"\u00a0","key":"e_1_2_7_4_2"},{"doi-asserted-by":"publisher","key":"e_1_2_7_5_2","DOI":"10.1016\/0010-8545(91)80024-8"},{"key":"e_1_2_7_6_2","first-page":"19","volume-title":"Chemistry of Advanced Materials","author":"Cassoux P.","year":"1998"},{"doi-asserted-by":"publisher","key":"e_1_2_7_7_2","DOI":"10.1016\/S0038-1098(97)10194-6"},{"key":"e_1_2_7_8_2","first-page":"108","volume-title":"Quantum Theory of Solids","author":"Peierls R. 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