Highly Polarizable Triiodide Anions (I3(-)) as Cross-Linkers for Coordination Polymers: Closing the Semiconductive Band Gap.

From a hydrothermal reaction using CuI, KI, and 3,3'5,5'-tetramethyl-4,4'-bipyrazole (TMBP), the triiodide anion I3(-) has been integrated into the water-stable 2D coordination polymer Cu(TMBP)I3 (1). In contrast with other metal triiodide complexes, 1 features remarkably small distortions in the bond distances associated with the I3(-) units (i.e., the Cu-I and I-I bonds), which effectively link up the copper(I) centers into infinite CuI3 chains. The electronic band gaps and electrical conductivity data are also found to be consistent with the I3(-) ion acting as an effective linker across the copper(I) centers.

Synthesis of new copper cyanide complexes via the transformation of organonitrile to inorganic cyanide.

Hydrothermal reaction of diaminomaleonitrile and copper salts under different conditions resulted in copper cyanide coordination polymers {[Cu(H 2O)(NH 3) 4][Cu 3(CN) 5].H 2O} n ( 1), {(CH 3) 4N[Cu(H 2O)(NH 3) 4][Cu 4(CN) 7]} n ( 2), and {(CH 3OH 2) 2[Cu 2(CN) 3]} n ( 3). 1 and 2 are new mixed-valence Cu(I,II), two 3D organic-inorganic molecular framework complexes that exhibit ionic inclusion. 3 is an open copper cyanide framework hosting a guest molecule. Cyanides in 1, 2, and 3 are produced by in situ C-C bond cleavage of diaminomaleonitrile, and then the remaining product is oxidized to form an oxalate group. The potential porosity of the hydrated coordination polymer 3 was estimated using a computational method based on Connolly's algorithm.

In situ production of silver nanoparticles on an aldehyde-equipped conjugated porous polymer and subsequent heterogeneous reduction of aromatic nitro groups at room temperature.

In a metal-free procedure, chelating thiol groups and an electrophile react to assemble a robust, conjugated porous polymer with pendant aldehyde functionalities. These groups are able to reduce Ag(i) ions to generate, in situ, Ag(0) nanoparticles evenly dispersed in the polymer matrix. The Ag(0)-polymer composite enables selective reduction of aromatic nitro compounds as a heterogeneous catalyst, and can be conveniently recycled multiple times.

Reversible uptake of HgCl2 in a porous coordination polymer based on the dual functions of carboxylate and thioether.

Bifunctional tetrakis(methylthio)-1,4-benzenedicarboxylic acid and Pb2+ ions form a robust porous net featuring free-standing thioether groups that allow reversible uptake of HgCl2.