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Methods to incorporate kinetically inert metal nodes and highly basic ligands into single-crystalline metal–organic frameworks (MOFs) are scarce, which prevents synthesis and systematic variation of many potential heterogeneous catalyst materials. Here we demonstrate that metallopolymerization of kinetically inert Ru2 metallomonomers via labile Ag–N bonds provides access to a family of atomically precise single-crystalline Ru2-based coordination polymers with varied network topology and primary coordination sphere. [ABSTRACT FROM AUTHOR]

Atomistic control of the coordination environment of lattice ions and the distribution of metal sites within crystalline mixed‐metal coordination polymers remain significant synthetic challenges. Herein is reported the mechanochemical synthesis of a reticular family of crystalline heterobimetallic metal–organic frameworks (MOFs) is now achieved by polymerization of molecular Ru2[II,III] complexes, featuring unprotected carboxylic acid substituents, with Cu(OAc)2. The resulting crystalline heterobimetallic MOFs are solid solutions of Ru2 and Cu2 sites housed within [M3L2] phases. The developed mechanochemical strategy is modular and allows for systematic control of the primary coordination sphere of the Ru2 sites within an isoreticular family of materials. This strategy is anticipated to provide a rational approach to atomically precise mixed‐metal materials. [ABSTRACT FROM AUTHOR]

Reaction of LnCl3·6H2O with 5-aminotetrazole-1-acetic acid (Hatza) under the presence of KOH produced a set of new Ln(III)/atza complexes, [Ln(atza)2(CH3OH)(H2O)Cl][Ln = Pr (1), Nd (2), Sm (3)], [Ln(atza)2(H2O)3]Cl [Ln = Eu (4), Gd (5)], and [Tb(atza)2(H2O)4]Cl (6). These compounds were structurally characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. The complexes 1−3are isostructural and display two-dimensional frameworks, the isostructural complexes 4−5show one-dimensional (1D) structures, and complex 6forms a 1D framework. Furthermore, the luminescence properties of 4and 6were investigated at room temperature in the solid state. [ABSTRACT FROM AUTHOR]