A novel nanosized porous supramolecular nonanuclear complex [Pb₉(HL)₁₂Cl₂(ClO₄)](ClO₄)₃·15H₂O·a(solvent) (1·15H₂O·a(solvent)) is reported that was synthesized by electrochemical oxidation of a Pb anode under the ambient conditions in a CH₃CN:MeOH solution of N′-phenyl(pyridin-2-yl)methylene-N-phenylthiosemicarbazide (H₂L), containing [N(CH₃)₄]ClO₄ as a current carrier. The supramolecular aggregate of 1 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 1 differs significantly from that recently reported by us [Pb₂(HL)₂(CH₃CN)(ClO₄)₂]·2H₂O (2·2H₂O), which was obtained using a conventional synthetic procedure by reacting Pb(ClO₄)₂ with H₂L 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.

中文翻译：

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在电化学条件下获得的纳米级多孔超分子铅（II）-N′-苯基（吡啶-2-基）亚甲基-N-苯硫代氨基脲聚集体


据报道，在环境条件下，通过对 Pb 阳极在 N′-苯基（吡啶-2-基）亚甲基-N-苯硫代氨基脲 （H_{阿拉伯数字}L） 中，含有 [N（CH₃）₄]ClO₄ 作为电流载流子。1 的超分子聚集体由无数的 Pb···与相邻物质的硫羰基硫原子建立的 S 四特键 （TtBs），也通过 DFT 计算通过 ELF、Laplacian 和 RDG 特性的 2D 图进行了分析。此外，Pb···Cl TtBs 与中心 Cl^– 阴离子和 Pb···O TtB 与 ClO₄^– 阴离子的三个氧原子，被揭示出来。值得注意的是，1 的分子结构与我们最近报道的 [Pb₂（HL）₂（CH₃CN）（ClO₄）₂]·2H₂O （2·2H₂O） 明显不同，后者是使用常规合成程序通过将 Pb（ClO₄）₂ 与 H₂L 反应在同一 CH₃ 中获得的CN：MeOH 溶液，从而突出了电化学条件的关键作用。使用紫外-可见光谱法和分光荧光法在甲醇中研究复合物的光学特性。 发现该复合物在 304 nm 处激发时是发射的，产生大约 420 至 600 nm 的宽发射带，具有多个峰。CIE-1931 色度坐标计算为 （0.33， 0.24），表明发射位于色度图的白色区域。需要进一步研究以充分描述这种发射的来源。