The reductions of benzophenone and anthracene with dimeric magnesium(i) complexes lead to thermally stable magnesium ketyl and magnesium anthracene complexes, respectively; both have been structurally characterised.

The crystal structures of the self-assembled metallapentacycles [{Fe(5)(bptz)(5)(CH(3)CN)(10)} ⊂ 2SbF(6)][SbF(6)](8)(1) and [{Fe(5)(bmtz)(5)(CH(3)CN)(10)} ⊂ SbF(6)][SbF(6)](9)(2) with the π-acidic ligands bptz (3,6-bis(2-pyridyl)-1,2,4,5-tetrazine) and bmtz (3,6-bis(2-pyrimidyl)-1,2,4,5-tetrazine), respectively, revealed cationic pentagons templated by [SbF(6)](-) ions. The short anion-π contacts established between the anions and the tetrazine rings play an important role in the stability of the pentagons.

A super-paddlewheel (comprised of two paddlewheels) metal-organic polyhedron (MOP) containing surface hydroxyl groups was synthesized and characterized. Condensation reactions with linear alkyl anhydrides lead to new MOPs with enhanced solubility. As a result, the surface-modified MOP 4 was demonstrated as a homogeneous Lewis-acid catalyst.

Two families of cationic cyanide-bridged complexes, namely,{[Co(triphos)(CN)(2)](2)[M(MeOH)(4)]}(ClO(4))(2)([Co(2)M] M=Mn, Fe, Co, and Ni; triphos=1,1,1-tris((diphenylphosphino)methyl)ethane) and {[Co(triphos)(CN)(2)](2)[M(MeOH)(4)](2)}(ClO(4))(4)([Co(2)M(2)] M=Mn and Ni) have been prepared from reactions of [Co(II)(triphos)(CN)(2)] and M(ClO(4))(2).6H(2)O (M=Mn, Fe, Co, Ni) in methanol. The trinuclear complexes [Co(2)Mn],[Co(2)Fe], and [Co(2)Co], as well as both new tetranuclear complexes [Co(2)Mn(2)] and [Co(2)Ni(2)], exhibit antiferromagnetic coupling between metal centers. In contrast, the [Co(2)Ni] is characterized by ferromagnetic interactions between the Co(II) and Ni(II) centers. The magnetic behavior for these complexes was investigated by DFT calculations and was found to derive from overlap patterns of the different magnetic orbitals as influenced by the angles of the cyanide bridges.

A NbO-type metal-organic framework, PCN-46, was constructed based on a polyyne-coupled di-isophthalate linker formed in situ. Its lasting porosity was confirmed by N(2) adsorption isotherm, and its H(2), CH(4) and CO(2) adsorption capacity was examined at 77 K and 298 K over a wide pressure range (0-110 bar).

Reactions between the [M(III)(CN)(6)](3-)(M = Fe and Co) anions and the mononuclear complex [Co(II)(dppe)(2)(H(2)O)][BF(4)](2) result in the formation of two isostructural trinuclear clusters {[Co(II)(dppe)(2)](2)[M(III)(CN)(6)]}(BF(4)). Surprisingly, reactions of [Co(dppe)(2)(H(2)O)](BF(4))(2) and [Co(triphos)(CH(3)CN)(2)](BF(4))(2) with [Cr(CN)(6)](3-) yield the mononuclear complexes [Co(dppe)(2)(CN)](BF(4)) and [Co(triphos)(CN)(2)], respectively. In the former case, an unusual pentanuclear intermediate complex {[Co(II)(3)(dppe)(4)(MeCN)][Cr(III)(CN)(6)](2)} was isolated. The reaction was probed by solution IR spectroscopy, which revealed a gradual conversion of the nu(C identical withN) stretches of the starting materials to those of the CN-bridged intermediate and eventually to the single nu(C identical withN) stretch of the final mononuclear product. The loss of carbon-bound CN(-) ligands from [Cr(CN)(6)](3-) occurs on a sufficiently slow time-scale for observation of varying degrees of cyanide linkage isomerism in the trigonal bipyramidal complex {[Co(tmphen)(2)](3)[Cr(CN)(6)](2)}; the study was aided by the use of different Co(II) starting materials. Results obtained by a combination of X-ray crystallography, infrared spectroscopy, and magnetometry provide unequivocal evidence that the presence of certain Lewis acids (e.g., Co(II) in this work and Fe(II) ions and BPh(3) in previously reported studies) promote the process of cyanide linkage isomerism, which, in the case of Co(II) species, leads to facile labilization of cyanide ligands from the [Cr(CN)(6)](3-) anion.

This article is a part of our efforts to control the magnetic anisotropy in cyanide-based exchange-coupled systems with the eventual goal to obtain single-molecule magnets with higher blocking temperatures. We give the theoretical interpretation of the magnetic properties of the new pentanuclear complex {[Ni(II)(tmphen)(2)](3)[Os(III)(CN)(6)](2)}.6CH(3)CN (Ni(II)(3)Os(III)(2) cluster). Because the system contains the heavy Os(III) ions, spin-orbit coupling considerably exceeds the contributions from the low-symmetry crystal field and exchange coupling. The magnetic properties of the Ni(II)(3)Os(III)(2) cluster are described in the framework of a highly anisotropic pseudo-spin Hamiltonian that corresponds to the limit of strong spin-orbital coupling and takes into account the complex molecular structure. The model provides a good fit to the experimental data and allows the conclusion that the trigonal axis of the bipyramidal Ni(II)(3)Os(III)(2) cluster is a hard axis of magnetization. This explains the fact that in contrast with the isostructural trigonal bipyramidal Mn(III)(2)Mn(II)(3) cluster, the Ni(II)(3)Os(III)(2) system does not exhibit the single-molecule magnetic behavior.

Pentanuclear cyanide-bridged clusters of the general formula {[M(tmphen)(2)](3)[M'(CN)(6)](2)}(tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline) have been under investigation in our laboratories for a number of years. These related molecules are conveniently prepared by a building block approach that involves the reaction of mononuclear {M(tmphen)(2)X(2)}(0/2+) species (M = Cr, Mn, Fe, Co, Ni, Zn; X = anion, solvent) with [M'(CN)(6)](3-) anions (M'= Cr, Mn, Fe, Co, Os). The resulting trigonal-bipyramidal (TBP) clusters, consisting of M and M' centers in the equatorial and axial positions, respectively, exhibit diverse properties including those that had previously been observed only for Prussian blue extended phases; these properties include single-molecule magnetism, spin crossover, charge-transfer-induced spin transitions, cyanide linkage isomerism, and magnetic coupling through diamagnetic metal ions. Given that a series of clusters with identical axial cyanometallate units can be prepared, we have been able to establish trends in magnetic coupling for families of clusters with different equatorial metal ions. The crystal packing of the clusters, which involves supramolecular pi-stacking interactions, reveals the origin of the observed differences in the coordination environments and, in several cases, the physical properties of the metal ions in the equatorial sites. Recent work has focused on the use of these molecules as building blocks for magnetic chains and the incorporation of highly anisotropic 5d metal ions such as Os(III) into the TBP core. Such comprehensive studies of small clusters are valuable for understanding and modeling the magnetic behavior of more complicated cyanide materials.

The hexacyanoosmate(iii) anion was used to prepare a pentanuclear cyanide bridged molecular cluster with ligand-protected Ni(ii) ions as well as the corresponding Prussian blue phase from a reaction with aqueous Ni(ii) ions.

Removal of methanol molecules from the interstices of a metal-organic framework based on a 2-D hexagonal Mn(II)-TCNQF(4) net results in stronger magnetic interactions and leads to a glassy magnetically ordered state; the magnetic behavior can be reversibly cycled upon solvation-desolvation of the material.