Multifunctional, defect-engineered metal-organic frameworks with ruthenium centers: sorption and catalytic properties.

A mixed-linker solid-solution approach was employed to modify the metal sites and introduce structural defects into the mixed-valence Ru(II/III) structural analogue of the well-known MOF family [M3(II,II)(btc)2] (M=Cu, Mo, Cr, Ni, Zn; btc=benzene-1,3,5-tricarboxylate), with partly missing carboxylate ligators at the Ru2 paddle-wheels. Incorporation of pyridine-3,5-dicarboxylate (pydc), which is the same size as btc but carries lower charge, as a second, defective linker has led to the mixed-linker isoreticular derivatives of Ru-MOF, which display characteristics unlike those of the defect-free framework. Along with the creation of additional coordinatively unsaturated sites, the incorporation of pydc induces the partial reduction of ruthenium. Accordingly, the modified Ru sites are responsible for the activity of the "defective" variants in the dissociative chemisorption of CO2, the enhanced performance in CO sorption, the formation of hydride species, and the catalytic hydrogenation of olefins.

Bis[chloridobis(1,10-phenanthroline)copper(II)] penta-cyanido-nitro-soferrate(II) di-methyl-formamide monosolvate.

The title complex [CuCl(C12H8N2)2]2[Fe(CN)5(NO)]·C3H7NO, consists of discrete [Cu(phen)2Cl](+) cations (phen is 1,10-phenanthroline), [Fe(CN)5NO](2-) anions and one di-methyl-formamide (DMF) solvent mol-ecule of crystallization per asymmetric unit. The Cu(II) atom is coordinated by two phenanthroline ligands and one chloride ion in a distorted trigonal-bipyramidal geometry. The dihedral angle between the phen ligands is 77.92 (7)°. The cation charge is balanced by a disordered nitro-prusside counter-anion with the Fe(II) atom located on an inversion center with a slightly distorted octa-hedral coordination geometry. In the crystal, weak C-H⋯N and C-H⋯Cl hydrogen bonds connect anions and cations into a two-dimensional network parallel to (100). In addition, π-π stacking inter-actions are observed with centroid-centroid distances in the range 3.565 (2)-3.760 (3)Å. The di-methyl-formamide solvent mol-ecule was refined as disordered about an inversion center.

Tris(2,2'-bipyridine)-copper(II) penta-cyanido-nitro-soferrate(II) methanol disolvate monohydrate.

The title complex [Cu(C10H8N2)3][Fe(CN)5(NO)]·2CH3OH·H2O, consists of discrete [Cu(bpy)3](2+) cations (bpy is 2,2'-bipyridine), [Fe(CN)5NO](2-) anions and solvent mol-ecules of crystallization (two methanol mol-ecules and one water mol-ecules per asymmetric unit). The Cu(II) ion adopts a distorted octa-hedral environment, coordinated by six N atoms from three bpy ligands. The cation charge is balanced by a nitro-prusside counter-anion, which has a slightly distorted octa-hedral coordination geometry. In the crystal, anions and solvent mol-ecules are involved in O-H⋯N and O-H⋯O hydrogen bonds, which form chains along [100]. The cations are located between these chains.

Bis(2,9-dimethyl-1,10-phenanthroline)copper(I) penta-cyanido-nitro-soferrate(II).

The asymmetric unit of the title complex [Cu(C14H12N2)2]2[Fe(CN)5(NO)], consists of a [Cu(dmp)2](+) cation (dmp is 2,9-dimethyl-1,10-phenanthroline) and half an [Fe(CN)5(NO)](2-) anion. The anion is disordered across an inversion center with the Fe(II) ion slightly offset (ca 0.205Å) from the inversion center in the direction of the disordered trans-coordinating CN/NO ligands. The anion has a distorted octa-hedral coordination geometry. The Cu(I) ion is coordinated by two phenanthroline ligands in a distorted tetra-hedral geometry. The dihedral angle between the phenanthroline ligands is 77.16 (4) Å. In the crystal, the cations are connected to the anions by weak C-H⋯N hydrogen bonds. In addition, weak π-π stacking inter-actions are observed, with centroid-centroid distances in the range 3.512 (3)-3.859 (3) Å.

Tetra-kis(µ(2)-cyanido-κ(2)C:N)dicyanido-tetra-kis-[tris-(2-amino-eth-yl)amine-κ(3)N,N',N'',N''']tetra-copper(II)iron(II) bis[pentacyanidonitrosoferrate(II)] hexahydrate.

The asymmetric unit of the title complex, [Cu(4)Fe(CN)(6)(C(6)H(18)N(4))(4)][Fe(CN)(5)(NO)](2)·6H(2)O, comprises a complex [{Cu(tren)CN}(4)Fe(CN)(2)](4+) [tren is tris-(2-amino-eth-yl)amine] cation, which exhibits -1 symmetry with the terminal cyanide ligands oriented trans to each other, and two [Fe(CN)(5)(NO)](2-) nitroprussiate counter-anions. In the crystal, N-H⋯N hydrogen-bonding inter-actions are observed between H atoms on the primary amine groups of the tren ligand and the terminal cyanide groups of the nitro-prussiate counter-ions. The N atom in the terminal CN ligand of the cation is equally disordered over two positions. The structure also contains disordered lattice water mol-ecules. Their contribution was elimin-ated from the refinement using the procedure described by van der Sluis & Spek (1990 ▶).

Bis[(cyanido-κC)bis(1,10-phenanthroline-κ(2)N,N')copper(II)] pentakis-(cyanido-κC)nitro-soferrate(II) dimethyl-formamide monosolvate.

The title compound, [Cu(CN)(C(12)H(8)N(2))(2)](2)[Fe(CN)(5)(NO)]·C(3)H(7)NO, is formed of discrete [Cu(phen)(2)CN](+) cations (phen is 1,10-phenanthroline), nitro-prusside [Fe(CN)(5)(NO)](2-) anions and dimethyl-formamide (DMF) mol-ecules of crystallization. The metal atom has a distorted trigonal-bipyra-midal coordination environment, defined by four N atoms of two phen mol-ecules and a C atom of the cyanide group (in the equatorial position). The [Fe(CN)(5)(NO)](2-) anion was found to be disordered about (but not on) a crystallographic twofold rotation axis. Geometries were restrained to ideal values. The dimethyl-formamide solvent mol-ecule was found to be disordered about a crystallographic inversion centre.

Solvothermal growth of a ruthenium metal-organic framework featuring HKUST-1 structure type as thin films on oxide surfaces.

Phase-pure crystalline thin films of a mixed-valence Ru(2)(II,III) metal-organic framework with 1,3,5-benzenetricarboxylate (btc) as a linker were solvothermally grown on amorphous alumina and silica surfaces. Based on the Rietveld refinement, the structure of Ru-MOF was assigned to be analogous to [Cu(3)(btc)(2)] (HKUST-1).