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Exciton transfers in the two-dimensional and spin-canted antiferromagnet (C2H5NH3)2MnCl4 were studied by investigating the absorption spectra 6A1g4T2g(4D) of Mn2+. A magnon side band (exciton–magnon simultaneous excitation) which has an anomalous shape with the cutoffs at the low-energy as well as the high-energy sides was observed. This anomalous shape could be reproduced in calculation as magnon side band, considering both the intersublattice and intrasublattice exciton transfers. From the analysis of this band shape, the magnitudes of the intersublattice and intrasublattice exciton transfers are estimated to be 10.2 and 6.8 cm?1, respectively. In the case of simple antiferromagnets without spin canting, the intersublattice exciton transfer process is forbidden because of the spin angular momentum. However, in the case of (C2H5NH3)2MnCl4, the prohibition of the intersublattice exciton transfer is removed by the canted-spin arrangement.  相似文献   

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The reactions of ten metastable immonium ions of general structure R1R2C?NH+C4H9 (R1 = H, R2 = CH3, C2H5; R1 = R2 = CH3) are reported and discussed. Elimination of C4H8 is usually the dominant fragmentation pathway. This process gives rise to a Gaussian metastable peak; it is interpreted in terms of a mechanism involving ion-neutral complexes containing incipient butyl) cations. Metastable immonium ions ontaining an isobutyl group are unique in undergoing a minor amount of imine (R1R2C?NH) loss. This decomposition route, which also produces a Gaussian metastable peak, decreases in importance as the basicity of the imine increases. The correlation between imine loss and the presence of an isobutyl group is rationalized by the rearrangement of the appropriate ion-neutral complexes in which there are isobutyl cations to the isomeric complexes containing the thermodynamically more stable tert-butyl cations. A sizeable amount of a third reaction, expulsion of C3H6, is observed for metastable n-C4H9 +NH?CR1R2 ions; in contrast to C4H8 and R1R2C?NH loss, C3H6 elimination occurs with a large kinetic energy release (40–48 kJ mol?1) and is evidenced by a dish-topped metastable peak. This process is explained using a two-step mechanism involving a 1,5-hydride shift, followed by cleavage of the resultant secondary open-chain cations, CH3CH+ CH2CH2NHCHR1R2.  相似文献   

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Conclusions The authors have synthesized anilinium chloranilate (NH3C6H5)2(C6O4Cl2) (I) and acid ammonium chloranilate dihydrate NH4H5O2(C6O4C12) (II). By x-ray structural analysis they have established their crystal structures. In crystals of NH4H5O2(C6O4Cl2) they find the ion H5O 2 + with the unusual O-H-O bond length of 2.81 A. The anions of chloranilic acid in crystals (I) and (II) have equal charges but different structures.Translated from IzvestiyaAkademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 487–489, March, 1981.  相似文献   

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The analysis of the crystal structure of (C4H3SCH2NH3)2(CH3NH3)Pb2I7, displaying a well-ordered acentric inorganic Pb2I7(3-) bilayer, is reported, and compared to the related monolayer hybrid perovskite.  相似文献   

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In hexakis(m‐toluidinium) cyclo­hexaphosphate, 6C7H10N+·­P6O186?, the atomic arrangement is typical of a layer structure. Layers including the centrosymmetric P6O18 ring anions develop around the (100) planes at x = . The hydrogen‐bond distribution is described.  相似文献   

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[(C6H5CH2C5H4)2GdCl.THF]2 (1) and (C6H5CH2C5H4)2ErCl.THF (2) were prepared by the reaction of LnCl3 (Ln? Gd, Er) with benzylcyclopentadienyl sodium in THF and characterized by elemental analysis, IR, 1H NMR, 13C NMR, MS and thermal gravimetry. The crystal structures of both compounds were determined. Complex 1 is dimeric and its structure belongs to the monoclinic, P21/c space group with a=1.1432(2), b=1.2978(2), c=1.7604(3) nm, β=108.75(2), V=2.4732(9) nm3, Z=2(four monomers), Dc“1.54 g.cm?3. R=0.0342 and Rw“0.0362. Complex 2 is monomer and its structure belongs to the orthorhombic, P212121 space group with a=0.8645(2), b=1.1394(3), c=2.5289(4) nm, V=2.4919(9) nm3, Z=4, Dc“1.56 g.cm?3. R=0.0514, Rw“0.0529. The determination of the crystal structure shows that in complex 1 the benzyl groups on the cyclopentadienyls coordinated to Gd3+ are located in the opposite direction (139°); in complex 2 the benzyl groups on the cyclopentadienyls coordinated to Er3+ are located in the same direction (6.5°).  相似文献   

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Cis-dioxo-tungsten(Ⅵ) complex, (NH2CH2CH2NH2)[(NH2CH2CH2NH3)2WO2(NHC6H4NH)2]2·H2O is synthesized at room temperature by the reaction of sodium tungstate with o-phenylenediamine. The crystal structure of complex was determined by X-ray diffraction structural analysis. The results show that complex belongs to monoclinic system with space group P21/ c, a=0.712 8(2) nm, b=3.081 1(10) nm, c=0.981 9(3) nm, β=102.615(4)°, V=2.104 4(11) nm3, Z=2, μ=55.26 cm-1, F(000)=1 176. Compared the complex with its analogous biomimetic complexes of the cofactor of molybdoenzymes and tungstoenzymses, it is found that the variance of the coordination atoms and the metal ions center have no influence on the coordination feature, and exhibits distored octahedral coordination with cis-dioxo o-phenylenediamine. CCDC: 252834.  相似文献   

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鲁晓明  宋富根  王波  李丽 《无机化学学报》2005,21(11):1687-1690
Cis-dioxo-catecholatotungsten(Ⅴ) complex (NH2CH2CH2NH3)4[WO2(OC6H4O)2]2(NH3CH2CH2NH3)·H2O (1) was synthesized at room temperature by the reaction of tetrabutyl ammonium decatungstate with catechol in the mixed solvent of CH3OH, CH3CN and NH2CH2CH2NH2. The crystal structure of complex was determined by X-ray diffraction structural analysis. The results show that complex belongs to monoclinic system with space group P21/c,a=0.712 8(3) nm, b=3.082 3(11) nm, c=0.982 8(4) nm, β=102.639(6)°, V=2.106 8(14) nm3, Z=2, R1=0.062 8, wR2=0.183 7. Compared the complex with its analogous complexes (NH2CH2CH2NH3)3[MoO2(OC6H4O)2], it is found that the coordination structure of W have no changes in the processing of electron transfer of tungsten-containing enzymes from the result of the similarity of the EPR spectra of the complexes and flavoenzyme from milk. CCDC: 272937.  相似文献   

11.
The dewetting behavior of thin (about 30 nm) polystyrene (PS) films filled with different amount of (C(6)H(5)C(2)H(4)NH(3))(2)PbI(4) (PhE-PbI(4)) on the silicon substrate with a native oxide layer was investigated. For different additive concentrations, PhE-PbI(4) showed different spatial distributions in the PS films, which had a strong influence on the film wettability, dewetting dynamics, and mechanism. With 0.5 wt % additive, PhE-PbI(4) formed a noncontinuous diffusion layer, which caused a continuous hole nucleation in the film. With about 1 wt % additive, a continuous gradient distribution layer of PhE-PbI(4) formed in the film, which inhibited the dewetting. When the concentration is higher (2 wt %), large PhE-PbI(4) aggregates, in addition to the PhE-PbI(4) continuous layer, formed in the film. These large aggregates (larger than radius of gyration of PS) migrated to the interface, resulting in the hole nucleation and eventually the complete dewetting of the film.  相似文献   

12.
Ultra-thin films of the two-dimensional layered perovskites [NH3(CH2)12NH3]PbX4 (X = Br, I) with the quantum confinement effect have been fabricated by a convenient self-assembly method.  相似文献   

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1 INTRODUCTION Palladium (Ⅱ) coordination and organometallic compounds usually show square planar environments at the metal center[1], and have experienced an im- portant development in the past years due to their acting as intermediates in different types of catalytic reactions and numerous applications in organic synthesis[2]. Although palladium plays an increase- ingly recognized role as a biometal[3], little is known about the structure and function of palladium compounds in living …  相似文献   

14.
An unusual two-dimensional zinc phosphate with pendant phosphate groups, projecting into the inter-lamellar space between the layers, has been synthesized and is shown to transform into a three-dimensional structure with 16-membered bifurcated channels, giving evidence for the building up process in the formation of open-framework structures.  相似文献   

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尹汉东  王传华  邢秋菊 《结构化学》2004,23(10):1127-1132
1 INTRODUCTION The chemistry of organotin(IV) complexes was extensively studied due to their biological activity and coordination chemistry[1~7]. More recently, phar- maceutical properties of alkyltin(IV) complexes with dithiocarbamate ligands have bee…  相似文献   

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Wang  Shutao  Wang  Enbo  Hou  Yu  Li  Yangguang  Wang  Li  Yuan  Mei  Hu  Changwen 《Transition Metal Chemistry》2003,28(6):616-620
A novel organic/inorganic hybrid molybdenum phosphate, [NH3(CH2CH2)2NH3]3[NH3(CH2CH2)2NH2]Na5-[Mo6O12(OH)3(PO4)(HPO4)3]2·4H2O (1), involving molybdenum presented in V oxidation, has been hydrothermally prepared and characterized by elemental analysis, i.r., u.v.–vis., x.p.s., t.g. and single crystal X-ray diffraction. The structure of the title compound (1) may be considered to consist of two [Mo6O12(OH)3(PO4)(HPO4)3] units bonded together with NaO6 octahedra, forming dimers. Further, these dimers connect with each other through four Na+ cations as bridges, giving rise to novel one-dimensional chain-like skeleton. Piperazines exist among inorganic chains acting as charge balancing cations.  相似文献   

18.
The reaction of heterobidentate 4-(dimethylamino)phenyldiphenylphosphine with labile cluster Rh6(CO)15(NCMe) yielding a new monosubstituted cluster Rh6(CO)15(Ph2PC6H4NMe2) was described. The reactions of the resulting cluster with GaX3 compounds were studied. The structure of all obtained compounds was completely characterized both in a solid phase and in a solution by X-ray diffraction analysis, mass spectrometry, and IR and polynuclear NMR spectroscopy.  相似文献   

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