Diverse Entangled Metal−Organic Framework Materials Incorporating Kinked Organodiimine and Flexible Aliphatic Dicarboxylate Ligands:  Synthesis, Structure, Physical Properties, and Reversible Structural Reorganization

Abstract

Hydrothermal synthesis has afforded a family of divalent metal adipate (adp) coordination polymers incorporating the kinked dipodal organodiimine 4,4'-dipyridylamine (dpa). As revealed by single-crystal X-ray diffraction, the structures of these materials are critically dependent on the metal coordination geometry, the carboxylate binding modes, and the conformations of the flexible adipate moieties. In all cases, hydrogen-bonding interactions imparted by the dpa tethers also play a structure-directing role. All materials were further characterized via infrared spectroscopy and elemental and thermogravimetric analysis. [Co(adp)(dpa)] (1) displays doubly interpenetrated three-dimensional (3-D) networks with a decorated alpha-Po-type (pcu) topology. In contrast, [Ni(adp)(dpa)(H2O)] (2) possesses a triply interpenetrated binodal cooperite-type (pts) framework, the highest level of interpenetration yet reported for this structure type. [Zn(adp)(dpa)].H2O (3) presents mutually inclined polycatenated 2-D graphitic layers consisting of neutral dimeric [Zn2(mu2-adp)2] kernels conjoined by dipodal dpa ligands. Compound 1 exhibited weak antiferromagnetic coupling between its carboxylate-bridged Co atoms, following Curie-Weiss behavior with Theta=-3.3 K. Compound 3 manifested blue light emission under ultraviolet excitation, as well as a reversible structural reorganization upon dehydration/rehydration.

Two new interpenetrating networks assembled from 5-methylisophthalic acid and bipyridyl ligand with copper(II) salts

“…Some other interpenetrated networks based on α-Po primitive cubic units have been previously reported [11]. The structures of 1 and 2 reported in this contribution is somewhat similar with some of the reported complexes such as [Cd (glutarate)(bpe)] [12] or [Co(adipate)(bpe)] [13].…”

Metal-dependent dimensionality in coordination polymers of a semi-rigid dicarboxylate ligand with additional amide groups: Syntheses, structures and luminescent properties

“…The PtS networks are common in metal-organic frameworks with interpenetrating structures [54][55][56][57][58]. However, in this case, the structure is not self dual owing to the small ring without enough length for interpenetration [59][60][61].…”

Tunable structures aroused by cation exchange reaction of solvent-mediated mechanism

“…In addition, the determination of Scanning Electron Microscope and Energy-Dispersive X-ray Spectrometry reveals that the exchange is a recurrent dissolving-exchange-crystallization process of solventmediated mechanism. This work provides a new effective tactic of adjusting molecular structures.In recent years, the construction of metal-organic frameworks (MOFs) has received remarkable attention due to their potentially applications in the areas of magnetism, molecular separation, catalysis, luminescence, sorption, and so on [1][2][3][4][5][6][7][8]. Generally, various frameworks can be obtained by tuning several factors, such as ligands, anions, templates, temperatures, and geometric requirements of metals [9][10][11][12][13][14][15][16].…”