The field of inorganic open-framework materials is dominated by aluminosilicates and phosphates. The metal carboxylates have emerged as an important family in the last few years. This family includes not only mono- and dicarboxylates of transition, rare-earth, and main-group metals, but also a variety of hybrid structures. Some of the carboxylates possess novel adsorption and magnetic properties. Dicarboxylates and related species provide an effective means of designing novel hybrid structures with porous and other properties. In some of these structures, the dicarboxylate acts as a linker between two inorganic units. Hybrid nanocomposites are also of particular note, for example, cadmium oxalate host lattices that can accommodate extended alkali-metal halide structures. This Review discusses the synthesis, structure, and properties of various types of open-framework metal carboxylates.

Metal carboxylates with open architectures.

Several important solvothermal (including hydrothermal) in situ metal/ligand reactions and their mechanisms, including dehydrogenative carbon−carbon coupling, hydroxylation of aromatic rings, cycloaddition of organic nitriles with azide and ammonia, transformation of inorganic and organic sulfur, as well as the CuII to CuI reduction, are outlined in this Account. The current progress clearly demonstrates the important potential of such reactions in the crystal engineering of functional coordination compounds and one-pot synthesis of some unusual organic ligands that are inaccessible or not easily obtainable via conventional methods, thereby substantiating our expectation that a new bridge has been created between coordination chemistry and synthetic organic chemistry.

Solvothermal in situ metal/ligand reactions: a new bridge between coordination chemistry and organic synthetic chemistry.

Molecular recognition is typically associated with molecules in solution, but such events are also responsible for organizing molecules in the solid state. Translating principles of molecular recognition to solid-state assembly of heteromeric molecular solids is of key importance to the development of versatile, reliable and practical supramolecular synthesis. In this article we provide an overview of some modular and transferable strategies for the synthesis of binary and ternary supermolecules and co-crystals based upon a hierarchy of intermolecular interactions, notably hydrogen bonds.

Building co-crystals with molecular sense and supramolecular sensibility

Crystal engineering of Cu-containing metal-organic coordination polymers under hydrothermal conditions

Six tetranuclear cadmium(II) complexes, Na[Cd4(hmt)2(H2O)6(dpa)4(NO3)]·8H2O (1), Na[Cd4(hmt)2(CH3OH)2(H2O)4(dpa)4I]·8H2O (2), Na[Cd4(hmt)2(H2O)6(dpa)4Br]·8H2O (3), Na2[Cd4(hmt)2(H2O)6(dpa)4(SCN)2]·4H2O (4), {Na[Cd4(hmt)2(H2O)6(dpa)4Cl](H2O)4}n (5), and {[Cd4(hmt)3(H2O)5(dpa)4](H2O)10}n (6) (hmt = hexamethylenetetramine, H2dpa = diphenic acid), were synthesized by reactions of H2dpa, hmt, and CdX2 (X = NO3-, I-, Br-, Cl-, SCN-, and OAc-). All the complexes contain a basic unit [Cd4(dpa)4], in which four dpa ligands in a chelating bis-bidentate coordination mode link two six-coordinate and two seven-coordinate cadmium(II) centers. The research result demonstrates that the nature of the counterions has an important effect on the assembly process of neutral and anionic mixed ligands with metal ions. In 1−3, NO3-, I-, or Br- bridges the two seven-coordinate CdII centers of the unit to form a discrete tetranuclear molecule with a cis-conformation and hmt as a terminal ligand coordinated to each of the two six-c...

Anion Effect on the Structural Conformation of Tetranuclear Cadmium(II) Complexes

The first oxalato and isonicotinato mixed-ligand guest-inclusion open-framework coordination polymer {[(H2O)2(oxa)Zn2(IN)2]·2(H2O)} was synthesized from a chemical rearrangement of isonicotinate to oxalate under hydrothermal conditions:  space group, P21/c; a = 8.302(1), b = 15.557(2), c = 7.344 (1) A, β = 94.351(1)°, U = 945.8(1) A3, Z = 2.

An Unforeseen Chemical Rearrangement of Pyridinecarboxylate to Oxalate under Hydrothermal Conditions Afforded the First Oxalato and Isonicotinato Mixed-Ligand Guest-Inclusion Coordination Polymer

Unexpected nicotinate zwitterions formed under hydrothermal conditions self-assembled into two-dimensional (2D) herringbone networks via hydrogen-bonding. The charges on the 2D zwitterion network are balanced by the counter polyiodide anions. The polyiodide species are sandwiched with 2D zwitterion networks. The zwitterion network structure is stable up to 150 °C.

The first nicotinate zwitterions self-assembled into 2D herringbone networks via hydrogen-bonding and sandwiched with polyiodide species

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An Unforeseen Chemical Rearrangement of Pyridinecarboxylate to Oxalate under Hydrothermal Conditions Afforded the First Oxalato and Isonicotinato Mixed-Ligand Guest-Inclusion Coordination Polymer

The first nicotinate zwitterions self-assembled into 2D herringbone networks via hydrogen-bonding and sandwiched with polyiodide species