Dimensionality Control in Crystalline Zinc(II) and Silver(I) Complexes with Ditopic Benzothiadiazole-Dipyridine Ligands

Three 2,1,3-benzothiadiazole-based ligands decorated with two pyridyl groups, 4,7-di(2-pyridyl)-2,1,3-benzothiadiazol (2-PyBTD), 4,7-di(3-pyridyl)-2,1,3-benzothiadiazol (3-PyBTD) and 4,7-di(4-pyridyl)-2,1,3 benzothiadiazol (4-PyBTD), generate ZnII AgI complexes a rich structural variety: [Zn(hfac)2(2-PyBTD)] 1, [Zn2(hfac)4(2-PyBTD)] 2, [Ag(CF3SO3)(2-PyBTD)]23, [Ag(2-PyBTD)]2(SbF6)24, [Ag2(NO3)2(2-PyBTD)(CH3CN)] 5, [Zn(hfac)2(3-PyBTD)] 6, [Zn(hfac)2(4-PyBTD)] 7, [ZnCl2(4-PyBTD)2] 8 [ZnCl2(4-PyBTD)] 9 (hfac = hexafluoroacetylacetonato). The nature of the resulting (discrete species or coordination polymers) is influenced by relative position nitrogen atoms, starting metal precursors, as well synthetic conditions. Compounds 1 are mononuclear 3 4 binuclear species. 7 1D polymers, while compound 5 2D polymer, ions being bridged 2-PyBTD nitrato ligands. solid-state architectures sustained intermolecular π–π stacking interactions established between group benzene ring from moiety. 7–9 show luminescence in visible range. Density Functional Theory (DFT) Time Dependent (TD-DFT) calculations have been performed on 2 order to disclose electronic transitions an insight modulation photophysical properties upon complexation.