Four Honeycomb Metal–Organic Frameworks with a Flexible Tripodal Polyaromatic Acid

• Published in: Crystal growth & design Vol. 13; no. 4; pp. 1429 - 1437
• Main Authors: Zhan, Chao, Zou, Chao, Kong, Guo-Qiang, Wu, Chuan-De
• Format: Journal Article
• Language: English
• Published: Washington,DC American Chemical Society 03.04.2013
• Subjects: Condensed matter: electronic structure, electrical, magnetic, and optical properties; Condensed matter: structure, mechanical and thermal properties; Cross-disciplinary physics: materials science; rheology; Exact sciences and technology; Materials science; Optical properties and condensed-matter spectroscopy and other interactions of matter with particles and radiation; Organic compounds; Other materials; Photoluminescence; Physics; Specific materials; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; Metal organic framework; Honeycomb lattices; Organometallic compounds; Photoluminescence; Topology; Acetates; Coordination polyhedron; Macrocycle; Magnetic susceptibility; Monocrystals; Transition elements; Copper sulfide; Ligands; Microstructure; Honeycomb structures; X-ray diffraction analysis; Magnetic properties
• ISSN: 1528-7483; 1528-7505
• DOI: 10.1021/cg301161c

Reaction of 4,4′,4″-{[(2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene)]tris(oxy)}tribenzoic acid (H3TCM) with Mn2+, Cu2+, and Co2+ salts afforded four interesting metal–organic frameworks (MOFs), [Mn2(TCM)Cl(H2O)3]·3DMF·3CH3OH (1), [Mn4(TCM)2(CH3COO)2(DMF)5]·4CH3OH (2), [Cu2(TCM)(CH3COO)(DMF)(H2O)]·2DMF·3CH3OH (3) and [Co3(TCM)2(H2O)5]·5DMF·3CH3OH (4). Single crystal X-ray diffraction analysis revealed that the four structures based on the flexible TCM tripod consist of honeycomb lattices with different metal–ligand macrocycles. The assembly of the metal–ligand macrocycles and framework topologies is dependent on the coordination geometries of transition metal cations. The two-dimensional coordination network of 1 was further connected by an auxiliary acetate ligand to give rise to a three-dimensional honeycomb network of 2. The TCM ligand centered photoluminescences of these compounds are very sensitive to the coordination modes of the TCM ligands, the metal secondary building units (SBUs), and their microstructures. These MOFs also present interesting magnetic behaviors, as revealed by the study of the magnetic susceptibilities.