Evidence for the Formation of a RuIII−RuIII Bond in a Ruthenium Corrole Homodimer

Conformations and coordination schemes of carboxylate and carbamoyl derivatives of the tetraazamacrocycles cyclen and cyclam, and the relation to their protonation states

Abstract This paper discusses and rationalizes the metal coordination pattern of 12- and 14-membered tetraazamacrocyclic carboxylate and carbamoyl ligands based on the cyclen and cyclam framework in light of their acido–basic properties. Structural and protonation data are reviewed in order to illustrate the influence of the free ligand's protonation state and of the pH conditions during the complexation reaction on the final coordination mode of the metallic cations.

Evolution towards centrosymmetry of the nonlinear-optical materialRbTiOPO4in the temperature range 293–973 K: Alkaline displacements and titanyl deformations

The crystal structure of rubidium titanyl phosphate, ${\mathrm{RbTiOPO}}_{4}$ (space group ${\mathrm{Pna}2}_{1}$), has been refined at room temperature, and at 473, 673, 873, and 973 K, by using single-crystal x-ray-diffraction techniques. The data show a large anharmonic motion of the rubidium ions increasing with temperature. To describe the importance of this motion in the phase-transition procedure and in the ionic conductivity phenomenon, two models are developed. The study of the deviation to the centrosymmetric structure (space group Pnan) shows that the change towards centrosymmetry of the titanyl groups correlates directly with the observed variation of the second-harmonic generati…

New Synthesis oftrans-Disubstituted Cyclam Macrocycles – Elucidation of the Disubstitution Mechanism on the Basis of X-ray Data and Molecular Modeling

A new way to synthesize trans-disubstituted cyclam tetraazamacrocycles 1 is reported. The synthesis proceeds in three steps via the tricyclic 1,4,8,11-tetraazatricyclo[9.3.1.14,8]hexadecane system 2, which can be selectively dialkylated and hydrolyzed under basic conditions to give the final product 1. An understanding of the reactivity, based on the X-ray experimental electrostatic potential and molecular modeling of the 1,4,8,11-tetraazatricyclo[9.3.1.14,8]hexadecane macrotricycle, has permitted the elucidation of a new reaction pathway leading to the trans-disubstituted cyclam.

Photoinduced HS state in the first spin-crossover chain containing a cyanocarbanion as bridging ligand

A new polymeric approach, based on cyanocarbanion ligands, for the design of spin crossover (SCO) compounds led us to the compound [Fe(abpt)2(tcpd)] (1) (tcpd^2 = (C[C(CN)2|3)^2 , abpt = 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole) which has been characterised as the first SCO molecular chain involving a cyanocarbanion as bridging ligand. Gomez Garcia, Carlos Jose, Carlos.Gomez@uv.es

Contributions to the application of the transferability principle and the multipolar modeling of H atoms: electron-density study of L-histidinium dihydrogen orthophosphate orthophosphoric acid. I.

The electron density of L-histidinium dihydrogen orthophosphate orthophosphoric acid has been determined from X-ray and neutron diffraction data at low temperature (120 K). Topological analysis of the electron density has been used to analyse the effect of the multipolar refinement strategy on the electron-density model in the hydrogen-bonding regions. The electron density at low temperature has also been used to acquire high-quality experimental thermal parameters at room temperature using the transferability principle. Molecular vibrations, TLS and normal mode analysis are discussed and studied at both temperatures.

A polar/π model of interactions explains face-to-face stacked quinoid rings: a case study of the crystal of potassium hydrogen chloranilate dihydrate

International audience; The nature of interactions between face-to-face staggered stacked quinoid rings with pi-systems, observed with a short inter-ring centroid. centroid distance, is analyzed by experimental and theoretical methods. Charge density studies based on X-ray diffraction and DFT calculations, complemented by impedance spectroscopy, were employed to define the electronic and structural characteristics of the quinoid rings responsible for their interactions within the crystal packing. The crystal packing is mainly stabilized by strong electrostatic interactions between the K+ cation and the hydrogen chloranilate anion. The proximity and orientation of the stacked quinoid rings i…

ChemInform Abstract: Synthesis and Electrode Reactions of Difluorogermanium(IV) Porphyrins. Molecular Stereochemistry and Crystal Structure of Difluoro-(2,3,7,8,12,13,17,18-octaethylporphyrinato)germanium(IV).

The difluorogermanium(IV) porphyrins [GeF2(P)][P = 2,3,7,8,12,13,17,18-octaethylporphyrinate(2–)(oep), 5,10,15,20-tetraphenylporphyrinate(2–)(tpp), or 5,10,15,20-tetra-p-tolylporphyrinate(2–)(tptp)] have been prepared by reacting hydrogen fluoride with the appropriate dichloro derivative [GeCl2(P)]. The complexes were characterized by elemental analysis, 1H n.m.r., i.r., and u.v.–visible spectroscopy. The electrochemical behaviour was investigated in non-aqueous media while spectroelectrochemistry and e.s.r. were used to characterize the oxidized and reduced complexes. Each complex could be reversibly oxidized or reduced by one electron. In each case these electron additions or abstractions…

Cyanocarbanion-based spin-crossover materials: photocrystallographic and photomagnetic studies of a new iron(II) neutral chain

International audience; A new iron(II) chain of formula [Fe(abpt)(2)(tcpd)] [1; (tcpd)(2-) = [C(10)N(6)](2-) = (C[C(CN)(2)](3))(2-) = 2-dicyanomethylene-1,1,3,3-tetracyanopropanediide anion, abpt = 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole] has been synthesized and characterized by IR spectroscopy, detailed variable-temperature single-crystal X-ray diffraction, magnetic and photomagnetic measurements. The crystal structure determination of 1 reveals a one-dimensional structural architecture in which the (tcpd)(2-) cyanocarbanion acts as a μ(2)-bridging ligand and the two abpt molecules act as chelating ligands. Detailed X-ray diffraction studies as a function of the temperature (293-10 K…

Order-disorder evolution in solid solutions of the NLO material KTiOPO : K Rb TiOPO and K Rb TiOPO in the temperature range 293-973 K

K0.88Rb0.12TiOPO4 and K0.465Rb0.535TiOPO4 solid solutions of the potassium titanyl phosphate (KTiOPO4, space group Pna21) family, are described at 293, 473, 673, 873 and at 973 K. Their high resolution structures are obtained by using accurate single-crystal X-ray diffraction techniques at high resolution, (sin A-1. Large anharmonic motion of alkaline ions increasing with temperature allows the evolution of the rubidium and potassium ions repartition in the two alkaline sites versus temperature. To describe this motion inducing ionic conductivity phenomenon and to determine accurately the order-disorder evolution, two alkaline site refinement models are developed and discussed. A thermodyna…

Behaviour of the non-linear optical material KTiOPO4in the temperature range 293-973 K studied by x-ray diffractometry at high resolution: alkaline displacements

The crystal structure of potassium titanyl phosphate, KTiOPO4 (space group Pna21), has been refined at room temperature, at 673 K, and at 973 K, by using accurate single-crystal x-ray diffraction techniques at high resolution (dmin = 0.35 A). The data show a large amount of anharmonic motion of the potassium ions, increasing with temperature. To describe this motion, two models are developed: a normal refinement including potassium anharmonic thermal displacement parameters, which describes the average motion of the alkaline sites, and another model in which the potassium sites are split within the harmonic approximation and the displacements of the potassium ions versus temperature are des…

Synthesis, characterization and electrochemistry of bismuth porphyrins: X-ray crystal structure of (OEP)Bi(SO3CF3)

The metalation of several free base porphyrins by the bismuth salts Bi(NO3)3 and Bi(SO3CF3)3 in DMF or pyridine is described. The resulting stable Bi(III) porphyrin complexes are characterized by electrochemistry, 1H NMR and UV-vis spectroscopy. The structure of ( OEP ) Bi ( SO 3 CF 3) was also determined by single-crystal X-ray diffraction and shows that ( OEP ) Bi ( SO 3 CF 3) exists as a dimer which is stabilized by electrostatic interactions in which the two [(OEP)Bi]+ cations are linked via oxygen atoms of two symmetrically related [Formula: see text] anions, leading to a heptacoordinated bismuth center. Electrochemical oxidation of ( OEP ) Bi ( SO 3 CF 3) and ( T p TP ) Bi ( SO3CF3 )…

On the application of an experimental multipolar pseudo-atom library for accurate refinement of small-molecule and protein crystal structures

International audience; With an increasing number of biomacromolecular crystal structures being measured to ultra-high resolution, it has become possible to extend to large systems experimental charge-density methods that are usually applied to small molecules. A library has been built of average multipole populations describing the electron density of chemical groups in all 20 amino acids found in proteins. The library uses the Hansen & Coppens multipolar pseudo-atom model to derive molecular electron density and electrostatic potential distributions. The library values are obtained from several small peptide or amino acid crystal structures refined against ultra-high-resolution X-ray diff…

Synthesis and electrode reactions of difluorogermanium(IV) porphyrins. Molecular stereochemistry and crystal structure of difluoro-(2,3,7,8,12,13,17,18-octaethylporphyrinato)germanium(IV)

The difluorogermanium(IV) porphyrins [GeF2(P)][P = 2,3,7,8,12,13,17,18-octaethylporphyrinate(2–)(oep), 5,10,15,20-tetraphenylporphyrinate(2–)(tpp), or 5,10,15,20-tetra-p-tolylporphyrinate(2–)(tptp)] have been prepared by reacting hydrogen fluoride with the appropriate dichloro derivative [GeCl2(P)]. The complexes were characterized by elemental analysis, 1H n.m.r., i.r., and u.v.–visible spectroscopy. The electrochemical behaviour was investigated in non-aqueous media while spectroelectrochemistry and e.s.r. were used to characterize the oxidized and reduced complexes. Each complex could be reversibly oxidized or reduced by one electron. In each case these electron additions or abstractions…

Synthesis and Electrochemistry of Aluminum Porphycenes. Crystal and Molecular Structure of Methyl-σ-Bonded Aluminum Etioporphycene

The synthesis and characterization of three monomeric aluminum porphycenes with anionic or σ-bonded axial ligands is reported. The investigated compounds are represented as ( EtioPc ) Al ( CH 3) and ( EtioPc ) AlX where EtioPc represents the dianion of etioporphycene and X = Cl − or OH −. Each synthesized complex was characterized by mass spectrometry. 1 H NMR, IR and UV-visible spectroscopies as well as by electrochemistry. Comparisons are made between the properties of complexes in the aluminum etioporphycene series and related chloro- or methyl σ-bonded Al ( III ) porphyrins containing octaethylporphyrin ( OEP ) or tetraphenylporphyrin ( TPP ) macrocycles. Comparisons are also made betw…

CCDC 1403137: Experimental Crystal Structure Determination

Related Article: Krešimir Molčanov, Jernej Stare, Biserka Kojić-Prodić, Claude Lecomte, Slimane Dahaoui, Christian Jelsch, Emmanuel Wenger, Ana Šantić, Bartosz Zarychta|2015|CrystEngComm|17|8645|doi:10.1039/C5CE01037C