pH-Specific Crystalline Binary and Ternary Metal–Organic Framework Materials of Pb(II) with (Di)Tricarboxylate Ligands and <i>N</i>,<i>N</i>′‑Aromatic Chelators. Structure, Architecture-Lattice Dimensionality, and Electronic Spectroscopic Property Correlations

Efforts to probe and delineate intricate structure–property relationships key to the development of crystalline Pb­(II)-containing metal–organic framework materials led to the design and pH-specific hydrothermal synthetic investigation of binary/ternary Pb­(II)-(di)­tricarboxylate ligand (succinic, glutaric, tricarballylic acids) systems in the presence of variable-nature aromatic N,N′-chelators bipyridine (bpy)/phenanthroline (phen). The arisen crystalline materials [Pb­(phen)­(suc)]n (1), [Pb3(phen)3­(glu)3]n­·7nH2O (2), [Pb3(tca)2]n (3), and [Pb2(phen)2­(tcaH)2]n­·nH2O (4) provide evidence for structural correlations linking the nature of ligands with Pb­(II) chemistry and the emerging crystalline-polymeric assemblies. Detailed physicochemical characterization (Fourier transform infrared spectroscopy, 13C-,207Pb-cross polarization magic angle spinning NMR, thermogravimetric analysis, luminescence) reveals distinct architecture, lattice dimensionality (2D-3D), and luminescence property correlations and identifies structural and electronic factors interweaving into the design of functional materials.为探究并阐明晶体态含铅(II)金属有机框架（metal–organic framework）材料开发所需的复杂结构-性能构效关系，本研究针对二元/三元铅(II)-二/三羧酸配体（丁二酸、戊二酸、丙烷三羧酸）体系，结合不同性质的芳香族N,N′-螯合剂联吡啶（bipyridine, bpy）/菲咯啉（phenanthroline, phen），开展了pH特异性水热合成研究。所获得的四种晶体材料分别为[Pb(phen)(suc)]ₙ(1)、[Pb₃(phen)₃(glu)₃]ₙ·7nH₂O(2)、[Pb₃(tca)₂]ₙ(3)以及[Pb₂(phen)₂(tcaH)₂]ₙ·nH₂O(4)，这些材料证实了配体性质与铅(II)配位化学及新型晶态聚合物组装体之间的构效关联。通过傅里叶变换红外光谱（Fourier transform infrared spectroscopy）、¹³C及²⁰⁷Pb交叉极化魔角旋转核磁共振（cross polarization magic angle spinning NMR）、热重分析（thermogravimetric analysis）以及发光性能表征等详细的物理化学表征手段，本研究揭示了不同晶体材料的骨架结构、晶格维度（2D-3D）与发光性能之间的明确关联，并阐明了贯穿功能材料设计全过程的结构与电子因素。