Coordination polymers are currently one of the hottest topics in Inorganic and Supramolecular Chemistry. This critical review summarizes the current state-of-the-art on electrical conductive coordination polymers (CPs), also named metal–organic frameworks (MOFs). The data were collected following two sort criteria of the CPs structure: dimensionality and bridging ligands (151 references).

Electrical conductive coordination polymers

Publisher Summary This chapter discusses construction of functional solid-state supramolecular metal complexes containing copper (I) and silver (I). The copper(I) and silver(I) ions are regarded as extremely soft acids favoring coordination to soft bases, such as ligands containing S and unsaturated N. Copper(I) and silver(I) complexes with these soft ligands give rise to an interesting array of stereochemistries and geometric configurations, with the coordination numbers of two to six all occurring. The most common stereochemistries for both ions are the linear two-coordinate and the tetrahedral four-coordinate geometries with some distortions of the environment, particularly in the presence of chelating type ligands, attributable to the spherical dl0 configuration. On the basis of resonance Raman spectra, the lowest excited state in the polymer is assigned to the Cu(I)-topyrazine metal-to-ligand charge-transfer excited state. Successful construction of multidimensional frameworks largely relies on ligand design to suit different geometries and coordination numbers of the metal ions.

Toward the Construction of Functional Solid-State Supramolecular Metal Complexes Containing Copper(I) And Silver(I)

Considerable progress has been made in recent years in controlling the assembly and orientations of individual molecules to create specific aggregates. It is the aim of this review to give an account of the latest developments in our groups with regard to construction of functional crystal metal complex supermolecules from self-assembly of copper(I) and silver(I) coordination compounds by intermolecular interactions as well as coordination bonds. Several approaches to such self-organization process have been highlighted. Spontaneous organization of hydrogen bonding and host–guest interactions in 3-cyano-6-methyl-2(1H)-pyridinone system result in the formation of three-dimensional channel structures and multi-fold interpenetrated diamondoid architectures by modification of hydrogen-bonding mode and distances. Control of effective aromatic stackings between polymeric chains assembles simple phenazine and benzothiadiazole building blocks into well-organized, multidimensional honeycomb and graphite structures...

Crystal Engineering of Multidimensional Copper(I) and Silver(I) Coordination Supermolecules and Polymers with Functions

Three compounds [4,4′-bipyH2][M(NCS)4] (M = Mn2+, Co2+ or Zn2+; 4,4′-bipy = 4,4′-bipyridine) were obtained from the reactions of 4,4′-bipy with M(SCN)2 in acidic solution and their crystal structures determined by single-crystal X-ray diffraction. All crystallise isomorphously in the chiral orthorhombic space group P21212. The tetrahedral [M(NCS)4]2− anions are inter-connected by S⋯S contacts (ca. 3.63 A) and are hydrogen bonded with the diprotonated [4,4′-bipyH2]2+ cations [N⋯S 3.241 A in 1; 3.235 A in 2; 3.239 A in 3] to form two-dimensional, highly wavy networks with hourglass-shaped cavities (ca. 12.3 A long; 9.4 A wide at the ends, 6.8 A at the waist). These two-dimensional networks are stacked with each other to furnish a channel accommodating the diprotonated [4,4′-bipyH2]2+ cations. The three organic–inorganic hybrid compounds are thermally stable with melting points above 230 °C. The powder second harmonic generation efficiencies were measured as moderate.

Organic–inorganic hybrid materials assembled through weak intermolecular interactions. Synthesis, structures and non-linear optical properties of [4,4′-bipyH2][M(NCS)4] (M = Mn2+, Co2+ or Zn2+; 4,4′-bipy = 4,4′-bipyridine)

An S⋯S contact assembled tetranuclear copper(I) complex with sulfur-rich ligand, 4,5-ethylenedithio-1,3-dithiole-2-thione

A unique coordination polymer consisting of two parallel C5H4S5 molecules bridging two silver(I) ions (C5H4S5=4,5-ethylenedithio-1,3-dithiole-2-thione)

Lang Ping Wu

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A unique coordination polymer consisting of two parallel C5H4S5 molecules bridging two silver(I) ions (C5H4S5=4,5-ethylenedithio-1,3-dithiole-2-thione)