Structural–Spectrochemical Correlations of Variable Dimensionality Crystalline Metal–Organic Framework Materials in Hydrothermal Reactivity Patterns of Binary–Ternary Systems of Pb(II) with (a)Cyclic (Poly)carboxylate and Aromatic Chelator Ligands

Efforts to comprehend the structural–spectrochemical correlations of crystalline metal–organic framework materials of Pb­(II) with (a)­cyclic and aromatic chelators linked to photoluminescent applications led to the hydrothermal pH-specific synthesis of crystalline materials [Pb­{H<sub>2</sub>BTC}­(phen)­(H<sub>2</sub>O)]<sub><i>n</i></sub>·2<i>n</i>H<sub>2</sub>O­(<b>1</b>), [Pb<sub>2</sub>{CBTC}]<sub><i>n</i></sub>(<b>2</b>), [Pb<sub>4</sub>(phen)<sub>8</sub>{CBTC}<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]<sub>3</sub>·70.3H<sub>2</sub>O­(<b>3</b>), and [Pb­{HCTA}­(H<sub>2</sub>O)<sub>2</sub>]<sub><i>n</i></sub>·<i>n</i>H<sub>2</sub>O­(<b>4</b>). X-ray studies showed that <b>1</b>–<b>4</b> exhibit unique architectures linked to 2D–3D coordination polymers formulated by Z-type units composed of Pb<sub>2</sub>O<sub>2</sub> cores, unusually high number of lattice–water molecules, and π–π and H-bond interactions. The contribution of the nature–structure properties of the aliphatic-(a)­cyclic organic (poly)­carboxylic/aromatic chelators-ligands to binary-ternary Pb­(II) reactivity weaves into the assembly of supramolecular networks, thereby providing clear structural–spectroscopic inter-relationships exemplifying the observed photoluminescent activity in a distinct MOF-linked fashion.