A Nanosized Porous Supramolecular Lead(II)–<i>N</i>′-phenyl(pyridin-2-yl)methylene-<i>N</i>-phenylthiosemicarbazide Aggregate, Obtained Under Electrochemical Conditions

A novel nanosized porous supramolecular nonanuclear complex [Pb₉(HL)₁₂Cl₂(ClO₄)](ClO₄)₃·15H₂O<i>·a</i>(solvent) (<b>1</b>·15H₂O<i>·a</i>(solvent)) is reported that was synthesized by electrochemical oxidation of a Pb anode under the ambient conditions in a CH₃CN:MeOH solution of <i>N</i>'-phenyl(pyridin-2-yl)methylene-<i>N</i>-phenylthiosemicarbazide (<b>H</b>_<b>2</b><b>L</b>), containing [N(CH₃)₄]ClO₄ as a current carrier. The supramolecular aggregate of <b>1</b> is enforced by a myriad of Pb···S tetrel bonds (TtBs) established with the thiocarbonyl sulfur atoms of adjacent species, which have been also analyzed by DFT calculations via 2D maps of ELF, Laplacian and RDG properties. Moreover, Pb···Cl TtBs with the central Cl^- anion, and Pb···O TtBs with the three oxygen atoms of the ClO₄^- anion, were revealed. Notably, the molecular structure of <b>1</b> differs significantly from that recently reported by us [Pb₂(HL)₂(CH₃CN)(ClO₄)₂]·2H₂O (<b>2</b>·2H₂O), which was obtained using a conventional synthetic procedure by reacting Pb(ClO₄)₂ with <b>H</b>_<b>2</b><b>L</b> in the same CH₃CN:MeOH solution, thus highlighting a crucial role of the electrochemical conditions. The optical characteristics of the complex were investigated using UV-vis spectroscopy and spectrofluorimetry in methanol. The complex was found to be emissive when excited at 304 nm, producing a broad emission band ranging from approximately 420 to 600 nm with multiple peaks. The CIE-1931 chromaticity coordinates, calculated as (0.33, 0.24), suggest that the emission lies in the white region of the chromaticity diagram. Further investigation is needed to fully characterize the origin of this emission.