Pablo Alborés

Structural and Magnetic Characterization of a μ-1,5-Dicyanamide-Bridged Iron Basic Carboxylate [Fe3O(O2C(CH3)3)6] 1D Chain

We are reporting an unprecedented example of a mu-1,5-dicyanamide (dca)-bridged iron basic carboxylate, [Fe3O(O2C(CH3)3)6], 1D chain. As revealed from X-ray determination, the Fe3O cores are arranged in a zigzag configuration along the chain and strictly aligned in the same plane. The chains are well-isolated by the bulky tert-butyl groups. Magnetic measurements showed that the Fe3O units are weakly antiferromagnetically coupled (J = -0.6 cm(-1)) through the dca ligand while possessing a well-isolated S = 1/2 spin ground state arising from competing antiferromagnetic interactions.

Class III Delocalization in a Cyanide‐Bridged Trimetallic Mixed‐Valence Complex

The NIR and IR spectroscopic properties of the cyanide-bridged complex, trans-[Ru(dmap)4 {(μ-CN)Ru(py)4 Cl}2 ](3+) (py=pyridine, dmap=4-dimethylaminopyridine) provide strong evidence that this trimetallic ion behaves as a Class III mixed-valence species, the first example reported of a cyanide-bridged system. This has been accomplished by tuning the energy of the fragments in the trimetallic complex to compensate for the intrinsic asymmetry of the cyanide bridge. Moreover, (TD)DFT calculations accurately predict the spectra of the trans-[Ru(dmap)4 {(μ-CN)Ru(py)4 Cl}2 ](3+) ion and confirms its delocalized nature.

Communication between Remote Moieties in Linear Ru−Ru−Ru Trimetallic Cyanide-Bridged Complexes

In this article, we report the structural, spectroscopic, and electrochemical properties of the cyanide-bridged complex salts trans-[(NC)Ru(II)(L)4(μ-CN)Ru(II)(py)4Cl]PF6 and trans-[Ru(II)(L)4{(μ-CN)Ru(II)(py)4Cl}2](PF6)2 (L = pyridine or 4-methoxypyridine). The mixed-valence forms of these compounds show a variety of metal-to-metal charge-transfer bands, including one arising from charge transfer between the remote ruthenium units. The latter is more intense when L = 4-methoxypyridine and points to the role of the bridging ruthenium unit in promoting mixing between the dπ orbitals of the terminal fragments.

cis-2,2′-Bipyrimidine-Bridged Polynuclear Complex: A Stairway-like Mixed-Valent {Fe4} Cluster

We report the first example of a polynuclear discrete coordination compound exhibiting only bpym bridges and containing a first-row d transition metal. A smooth self-assembly one-pot synthetic route, starting from simply FeCl(2) and FeCl(3) hydrates, allowed us to prepare a tetranuclear Fe(4) cluster with a stairway-like structure and the formula cis-{[(H(2)O)Cl(3)Fe(III)-μ(bpym)Fe(II)Cl(2)]}(2)-μ(bpym) (1) . All spectroscopic data suggest that complex 1 is a valence-localized mixed-valent Fe(II)-Fe(III) cluster with typical Mössbauer lines for both sites, which do not change with temperature. Reflectance spectroscopy did not allow one to distinguish an intervalence charge-transfer band. However, time-dependent density functional theory (DFT) calculations predict a weak high-energy Fe(II) → Fe(III) transition. Regarding the magnetic properties, the high-spin Fe(II) and Fe(III) ions interact in a weakly antiferromagnetic way with isotropic J constants of only a few wavenumbers as derived from direct-current susceptibility and magnetization data. Broken-symmetry DFT calculations support these observations.

Exchange coupling across the cyanide bridge: structural and DFT interpretation of the magnetic properties of a binuclear chromium(III) complex

The reaction of [Cr(CN)6]3- with a mixture of trans-[Cr(cyclam)(OH)2]Cl, [Cr(cyclam)(OH)Cl]Cl and [Cr(cyclam)Cl2]Cl affords the cyanide bridged dimer, trans-[HO-Cr(cyclam)-NC-Cr(CN)5]-. The tetraphenylphosphonium salt of the anion crystallizes in space group P2(1)/n and shows a bent arrangement of the Cr1-CN-Cr2 unit with the Cr1-CN bond angle at 166.9 degrees and CN-Cr2 at 160.32 degrees . The Cr2-O bond, trans to the hexacyanide fragment, is very short at 1.902 A. Two dimers are held together by two hydrogen bonds connecting the Cr2-OH group of each dimer with one of the NH groups of the cyclam ligand of an adjacent molecule, leading to an almost linear configuration. These dimers of dimers get packed parallel to each other, generating layers separated by the tetraphenylphosphonium cations. Four of the cyanide groups of the anion are engaged in H-bonds with the four water molecules present in the structure or with a NH group of the macrocycle of an adjacent molecule. From magnetic susceptibility measurements, the dimer was found to exhibit antiferromagnetic interaction between the Cr(III) centers with J=-16 cm(-1)(H=-2JS(A)S(B)). Structural and magnetic parameters have been calculated by density functional theoretical methods at the B3LYP level. The exchange coupling constant, J, calculated for the dimer at the X-ray geometry is -23.2 cm(-1) which is in excellent agreement with the experimental value.

Reactivity and spectroscopy of the {Ru(DMAP)5} fragment: an {Ru(NH3)5} analogue.

Reaction of trans-Ru(DMSO)4Cl2 with DMAP (DMAP = 4-dimethylaminopyridine) yields the yellow [Ru(DMAP)6](2+) cation in good yield. The crystal and molecular structure of [Ru(DMAP)6]Cl2.6CH3CH2OH was determined by X-ray diffraction methods. The complex crystallizes in the trigonal R3 space group with a = b = 16.373(1), c = 20.311(1) A, gamma = 120 degrees , and Z = 3 molecules per unit cell. The reaction of [Ru(DMAP)6](2+) in aerobic water gives the red [Ru(III)(DMAP)5(OH)](2+) cation. This complex shows a chemical behavior similar to [Ru(III)(NH3)5Cl](2+) and allows the preparation of a family of [Ru(DMAP)5L](n+) complexes. Their electronic properties indicate that the {Ru(II)(DMAP)5} fragment is a weaker pi-donor than {Ru(II)(NH 3)5}. Our density functional theory (DFT) calculations show that in {Ru(II)(DMAP)5} the DMAP ligands can compete for the pi electron density of the ruthenium making the fragment a weaker pi-donor.

A convenient synthesis of a 2,7-difunctional tetra(alkoxy)triphenylene involving 4,4′-diacetoxy-3,3′-dialkoxybiphenyl as a key precursor and its conversion to extended hybrid mesogenic compounds

A new rational pathway to 2,7-difunctionalised-β-hexa-substituted triphenylenes is presented, requiring less protection/deprotection and purification steps than more conventional synthetic procedures in the framework of the ‘biphenyl route’. Main improvements are deprotection via alkaline hydrolysis of an ester in ethanol/water medium instead of using toxic and pyrophoric reagents like lithium diphenylphosphide, and the use of easily prepared brominated precursors instead of iodinated reagents for biphenyl synthesis. 4,4′-Diacetoxy-3,3′-bis(hexyloxy)biphenyl has been synthesised under this scheme, and characterised by proton nuclear magnetic resonance (1H NMR) spectrometry, elemental analysis and single-crystal crystallography. It crystallises in the P-1 space group, and exhibits a layered structure built-up through dipolar, C–H … π and C–H … O=C non-covalent interactions. This compound has been oxidatively coupled with 1,2-bis(hexyloxy)benzene to yield 2,7-dihydroxy-3,6,10,11-tetrakis(hexyloxy)triphenylene, a non-mesogen key precursor for the synthesis of the corresponding liquid-crystalline 2,7-difunctional triphenylenes. Indeed, a reactive 2,7-difunctional mesogen was prepared and used to produce new triphenylene-siloxane hybrid monomeric, trimeric and polymeric mesogens. All of them exhibited columnar hexagonal (Colh) mesophases.

4,4'-Bis(N,N-diethylamino)-2,2'-bipyridine.

The title compound, C(18)H(26)N(4), contains two almost identical independent molecules that lie about inversion centres. Each molecule has a planar bipyridine nucleus and two terminal diethylamine groups oriented at almost right angles to the core. These diethylamine branches act as spacers, producing a very open structure with one of the lowest densities reported among related compounds. The most important intermolecular interactions are of the C-H...pi type, which connect non-equivalent moieties.

A complex containing three different kinds of Ru-N bonds: Ethoxydinitronitrosyl(N, N, N', N'-tetramethylethylenediamine-κ2N, N')ruthenium(II)

The octahedral title compound, [Ru(C(2)H(5)O)(NO)(NO(2))(2)(C(6)H(16)N(2))], crystallizes in the rhombohedral space group P3(1) with an ethoxy ligand axially coordinated trans to the nitrosyl ligand. The RuII ion is equatorially coordinated by a tetramethylethylenediamine group acting as a bidentate ligand, and to two nitro moieties whose planes are tilted with respect to the mean equatorial plane. Each nitrogen ligand bonded to the metallic centre has a different hybridization state.