New complexes constructed from in situ nitration of (1H-tetrazol-5-yl)phenol: synthesis, structures and properties

Nine new complexes, {[Zn3(L1)2(OH)2]·H2O}n (1), [Ag2(L1)]n (2), {[Co(HL1)2(H2O)4]·2H2O} (3), [Cu3(L1)2(OH)2(H2O)]n (4), {[Cu7(HL1)2(L1)6(H2O)6]·11.1H2O}n (5), {[Cu(L1)(H2O)3]·8H2O}n (6), [Ag2(L2)]n (7), [Ag8(L3)4(H2O)]n (8) and [Cu(L3)(H2O)2]n (9) [H2L1 = 2,6-dinitro-4-(1H-tetrazol-5-yl)phenol, H2L2 = 2,4,6-trinitro-3-(1H-tetrazol-5-yl)phenol, H2L3 = 2,4-dinitro-6-(1H-tetrazol-5-yl)phenol], have been solvothermally synthesized via in situ nitration from 4-(1H-tetrazol-5-yl)phenol, 3-(1H-tetrazol-5-yl)phenol and 2-(1H-tetrazol-5-yl)phenol precursors as well as nitrate salts as nitration reagents and structurally characterized by single-crystal X-ray diffraction, infrared spectroscopy (IR), elemental analysis, powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA). The structures of the complexes vary from 3D frameworks for 1, 4 and 7, 2D networks for 2, 5 and 8, 1D chains for 6 and 9, to a discrete 0D structure for 3, showing 2D supramolecular structures by interlayer π–π stacking. Topological classification of 2D and 3D architectures was performed, disclosing a variety of topological symbols: (42·6)2(44·62·88·10) for 1, (43)2(46·66·83) for 2, (46)2(412·612·84) for 4, (63) for 5 and (45·6)(47·63)(418·616·82) for 7. The contrast of 1–9 reveals that ligands and metal salts have important influences on adjusting the crystal structures; notably, the coordination modes of the ligands can also tune the structures of 4–6 which possess the same ligands and nitration agents. The solid-state UV-vis spectra and band gap energy of the nine complexes were investigated. In addition, the luminescence properties (for complexes 1–3, 7 and 8) and magnetic properties (for complexes 3–6 and 9) were also discussed.