Abstract: | This work presents an investigation on the positions of the substituent and N-donor auxiliary chelating ligand (bipy/phen) effect on engineering of crystalline architectures of four Pb(II) complexes with a pair of methyl-substituted 3-sulfobenzoic isomers: Pb(4-msba)(phen)(H2O)] (1), Pb(4-msba)(bipy)(H2O)]·H2O (2), Pb(5-msba)(phen)2]·9H2O (3), and Pb2(5-msba)2(bipy)2(H2O)2] (4) (4/5-msba?=?4/5-methyl-3-sulfobenzoate, phen?=?1,10-phenanthroline and bipy?=?2,2′-bipyridine). The lead(II) ions exhibit hemidirected geometry in 1–4. The positions of the methyl as well as the auxiliary chelating ligands influence coordination modes of the sulfonates and thus determine the architectures. As the position of methyl in aromatic ring changes from 4 to 5, the structures change from 2-D sheet-like compounds for 1 and 2 to 0-D dimeric species for 3 and 4. A water cluster (H2O)18 exists in 3, which further assembles into a water tape with a new pattern T4(3)4(3)10(3)A4. Complex 3 loses crystallinity rapidly in the open air and turns into Pb(5-msba)(phen)2]·2H2O (3A). Thermal stabilities and solid state fluorescent properties of 1, 2, 3A, and 4 have been studied. |