Abstract
Five new lead(II) sulfonate‐phosphonates, namely [Pb~3~(L)~2~(H~2~O)~2~]·4H~2~O (1), [Pb(HL)(phen)]·H~2~O (2), [Pb~6~(L)~4~(phen)~8~]·3H~2~O (3), [Pb~6~(L)~4~(phen)~10~]·2H~2~O (4), and [Pb~6~(L)~4~(4,4′‐bipy)(H~2~O)~2~]·2H~2~O (5; H~3~L = m‐HO~3~S‐C~6~H~4~‐PO~3~H~2~, phen = 1,10‐phenanthroline, 4,4′‐bipy = 4,4′‐bipyridine) have been prepared and structurally characterized. Compound 1 features a novel 3D framework in which 1D chains of Pb~3~O~4~ cluster units are further bridged by sulfonate‐phosphonate ligands, whereas compound 2 features a layer structure in which 1D chains of Pb~2~O~4~ clusters are further bridged by sulfonate‐phosphonate ligands. Compounds 3 and 4 represent the first zero‐dimensional lead(II) phosphonates and feature novel isolated hexanuclear lead(II) clusters in which six Pb^II^ ions are bridged by two tetradentate and two pentadentate phosphonate groups. Compound 5 features a 3D framework that is similar to that in compound 1 despite the different coordination modes for some sulfonate groups of the ligands. The main difference is that an aqua ligand in compound 1 is replaced by a nitrogen atom of the 4,4′‐bipy ligand, which results in the splitting of the large cavities in compound 1 into two small apertures in compound 5. Compounds 1 and 5 exhibit strong broad blue fluorescent emission bands at 398 and 420 nm, respectively.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)