Thermochromic effects in a Jahn-Teller active CuCl(4-)6 layered hybrid system.

The hybrid material copper (II) tetrachloro-bis(phenyl ethyl ammonium) (C6H5CH2CH2NH3)2CuCl4, or PEACuCl, has been investigated by temperature-dependent spectroscopic absorption experiments. The absorption bands observed in the near-infrared region (1.3-1.9 eV) generally exhibit redshifts with increasing temperature. The temperature-induced energy shifts of the spectral components are shown to be consistently related to temperature-induced Cu-Cl bond length changes. Additionally, the thermochromic color change is caused by a charge transfer band edge redshifting (in the visible region 2.0-2.8 eV) with increasing temperature. By comparison with similar Cu-based systems, it is suggested that this shift is caused by broadening and strengthening of the band.

Clostridium difficile in Dutch animals: their presence, characteristics and similarities with human isolates.

The presence and characteristics of Clostridium difficile were investigated in 839 faecal samples from seven different animal species in the Netherlands. The number of positive samples ranged from 3.4% (cattle) to 25.0% (dogs). Twenty-two different PCR ribotypes were identified. Among 96 isolates, 53% harboured toxin genes. All C. difficile isolates from pigs, cattle and poultry were toxinogenic, whereas the majority of isolates from pet animals consisted of non-toxinogenic PCR ribotypes 010 and 039. Ribotype 012 was most prevalent in cattle and ribotype 078 in pigs. No predominant ribotypes were present in horse and poultry samples. Overall, PCR ribotypes 012, 014 and 078 were the most frequently recovered toxinogenic ribotypes from animal samples. Comparison with human isolates from the Dutch Reference Laboratory for C. difficile at Leiden University Medical Centre (LUMC) showed that these types were also recovered from human hospitalized patients in 2009/2010, encompassing 0.8%, 11.4% and 9.8% of all isolates, respectively. Application of multiple-locus variable-number tandem-repeat analysis indicated a genotypic relation of animal and human ribotype 078 strains, but a clear genotypic distinction for ribotypes 012 and 014. We conclude that toxinogenic C. difficile PCR ribotypes found in animals correspond to PCR ribotypes associated with human disease in hospitalized patients in the Netherlands. Contrary to PCR ribotype 078, significant genetic differences were observed between animal and human PCR ribotype 012 and 014 isolates.

Evidence for differentiation in the iron-helicoidal chain in GdFe3(BO3)4.

A single-crystal X-ray structure study of gadolinium triiron tetraborate, GdFe3(BO3)4, at room temperature and at 90 K is reported. At room temperature GdFe3(BO3)4 crystallizes in a trigonal space group, R32 (No. 155), the same as found for other members of the iron borate family RFe3(BO3)4. At 90 K the structure of GdFe3(BO3)4 transforms to the space group P3(1)21 (No. 152). The low-temperature structure determination gives new insight into the weakly first-order structural phase transition at 156 K and into the related Raman phonon anomalies. The presence of two inequivalent iron chains in the low-temperature structure provides a new perspective on the interpretation of the low-temperature magnetic properties.

Polymorphism in pentacene.

Pentacene, C(22)H(14), crystallizes in different morphologies characterized by their d(001)-spacings of 14.1, 14.5, 15.0 and 15.4 A. We have studied the crystal structure of the 14.1 and 14.5 A d-spacing morphologies grown by vapour transport and from solution. We find a close correspondence between the 14.1 A structure reported by Holmes, Kumaraswamy, Matzeger & Vollhardt [Chem. Eur. J. (1999), 5, 3399-3412] and the 14.5 A structure reported by Campbell, Monteath Robertson & Trotter [Acta Cryst. (1961), 14, 705-711]. Single crystals commonly adopt the 14.1 A d-spacing morphology with an inversion centre on both molecules in the unit cell. Thin films grown on SiO(2) substrates above 350 K preferentially adopt the 14.5 A d-spacing morphology, with a slightly smaller unit-cell volume.

Synthesis, structural characterization, and transmetalation reactions of a tetranuclear magnesium silsesquioxane complex.

The reaction of a silsesquioxane trisilanol with methylmagnesium chloride leads to an unprecedented tetranuclear magnesium silsesquioxane complex 1 in high yield. The crystal structure shows an unusually short Mg-Cl bond, indicative of an electron-deficient magnesium atom; 1 has been used as transmetalation agent for the synthesis of metal silsesquioxane complexes. Transmetalation activity was low, but can easily be followed by multinuclear NMR. Crystal data for 1: C(78)H(142)Cl(2)Mg(4)O(26)Si(14).6(C(4)H(8)O), a = 15.744(1) A, b = 26.526(2) A, c = 16.917(1) A, beta = 113.229(2) degrees, monoclinic, P2(1)/n, Z = 2.

Hexagonal YMnO(3).

The crystal structure of hexagonal yttrium trioxomanganate has been determined at room temperature and at 180 K. It is isomorphous with LuMnO(3). The Mn displacement vector has a frustrated component in the ab plane and a ferroelectric part along the c axis. The net ferroelectricity is zero due to inversion twinning, with 1:1 twin fractions.

Spin-singlet clusters in the ladder compound NaV2O5

The space group of alpha(')-NaV2O5 turns below T(c) = 34 K from Pmmn with all V sites equivalent, into Fmm2 with three independent vanadium sites per layer. This is incompatible with models of charge ordering into V4+ and V5+. Our structure determination indicates that the phase transition consists of a charge ordering with three distinct valence states, formally V4+, V4.5+, and V5+. The singlet formation is not associated with dimerization on the spin ladder, but with the formation of spin clusters. Finally, we ascribe the quadrupling of the c axis to the large polarizability of the V2O5 skeleton.

Chiral overcrowded alkenes; asymmetric synthesis of (3S,3'S)-(M, M)-(E)-(+)-1,1',2,2',3,3',4,4'-octahydro-3,3',7,7'-tetramethyl-4, 4'-biphenanthrylidenes.

An asymmetric synthesis route towards (3S,3'S)-(M,M)-(E)-(+)-1,1',2, 2',3,3',4,4'-octahydro-3,3',7,7'-tetramethyl-4,4'-biphenanthrylidene was developed using the Evans procedure as a key step. The absolute configurations of the title compound and of its parent ketone were determined by CD spectroscopy and could be correlated with the stereochemical results of the asymmetric alkylation. Furthermore, a comparison was made with the known (3R,3'R)-(P,P)-(E)-(-)-1,1',2,2', 3,3',4,4'-octahydro-3,3',7,7'-dimethyl-4,4'-biphenanthrylidene. Finally, the X-ray crystallographic analysis of (3S,3'S)-(M, M)-(E)-(+)-1,1',2,2',3,3',4,4'-octahydro-3,3',7,7'-tetramethyl-4, 4'-biphenanthrylidene is presented.

Cationic and neutral diphenyldiazomethanerhodium(I) complexes as catalytically active species in the C-C coupling reaction of olefins and diphenyldiazomethane

Cationic rhodium(I) complexes cis-[Rh(acetone)2(L)(L')]+ (2: L = L'=C8H14; 3: L=C8H14; L'=PiPr3; 4: L=L'=PiPr3), prepared from [RhCl(C8H14)2]2] and isolated as PF6 salts, catalyze the C-C coupling reaction of diphenyldiazomethane with ethene, propene, and styrene. In most cases, a mixture of isomeric olefins and cyclopropanes were obtained which are formally built up by one equivalent of RCH=CH2 (R = H, Me, Ph) and one equivalent of CPh2. The efficiency and selectivity of the catalyst depends significantly on the coordination sphere around the rhodium(I) center. Treatment of 4 with Ph2CN2 in the molar ratio of 1:1 and 1:2 gave the complexes trans-[Rh(PiPr3)2(acetone)(eta1-N2CPh2)]PF6 (8) and trans-[Rh(PiPr3)2(eta1-N2CPh2)2]PF6 (9), of which 8 was characterized by X-ray crystallography. Since 8 and 9 not only react with ethene but also catalyze the reaction of C2H4 and free Ph2CN2, they can be regarded as intermediates (possibly resting states) in the C-C coupling process. The lability of 8 and 9 is illustrated by the reactions with pyridine and NaX (X=Cl, Br, I, N3) which afford the mono(diphenyldiazomethane)rhodium(I) compounds trans-[Rh(PiPr3)2(py)(eta1-N2CPh2)]PF6 (10) and trans-[RhX(eta1-N2CPh2)(PiPr3)2] (11-14), respectively. The catalytic activity of the neutral complexes 11 - 14 is somewhat less than that of the cationic species 8, 9 and decreases in the order Cl > Br> I > N3.

Asymmetric Synthesis of Overcrowded Alkenes by Transfer of Axial Single Bond Chirality to Axial Double Bond Chirality.

Optically active overcrowded alkenes were synthesized by employing bis-beta-naphthol as a chiral template during an intramolecular coupling reaction. The major isomer 2 has a unique helical structure with twisted and folded structural moieties. Removal of the chiral template afforded overcrowded thioxanthylidene 3 with 96 % ee, which indicates that no racemization or isomerization of the enantiomers took place.

Novel Organo-Substituted Cyclophosphazenes via Reaction of a Monohydro Cyclophosphazene and Acetyl Chloride.

A new olefin-substituted tetrachlorocyclotri-lambda(5)-phosphazene (NPCl(2))(2)NP(i)Pr{C[OC(O)Me]=CH(2)} (4) and an unique bicyclo-lambda(5)-triphosphazene [(NPCl(2))(2)NP(i)Pr](2)C(OH)Me (5) have been prepared from the reaction of MeC(O)Cl and (NPCl(2))(2)NP(i)PrH in the presence of Et(3)N. Exclusive formation of 4 could be achieved by using an excess of both Et(3)N and MeC(O)Cl. The phosphazene rings in 5 are bridged by one carbon atom. The presence of this C(OH)Me bridge induces an asymmetric environment which renders the isopropyl ligands no longer equivalent under NMR conditions. Crystals of 4 are monoclinic, space group P2(1)/n, with a = 13.158(1) Å, b = 9.555(1) Å, c = 14.859(1) Å, beta = 115.502(6) degrees, V = 1686.1(3) Å(3), and Z = 4. Crystals of 5 are monoclinic, space group P2(1)/c, with a = 13.255(2) Å, b = 12.050(2) Å, c = 16.280(2) Å, beta = 98.91(1) degrees, V = 2568.8(7) Å(3), and Z = 4.