Three new compounds of formula (Cp2∗Co)[Ni(dmit)2](1), (Cp2∗Mn)[Ni(dmid)2]·(CH3)2CO (2), and (Cp2∗Mn)2[Ni(dmid)2]2·C6H5CN (3) have been synthesised, and structurally and magnetically characterised (dmit2− = 1,3-dithiol-2-thione-4,5-dithiolato; dmid2− = 1,3-dithiol-2-one-4,5-dithiolato). Their structural features and magnetic behaviours are compared with those of (Cp2∗Mn)[Ni(dmit)2] and (Cp2∗Mn)[Ni(dmid)2]·CH3CN. The result of this is that the interactions between the Ni(dmit)2 units in 1 are of ferromagnetic-type, as suggested previously for (Cp2∗Mn)[Ni(dmit)2]. The change from acetonitrile to acetone when going from (Cp2∗Mn)[Ni(dmid)2]·CH3CN to 2 results in stronger ferromagnetic intermolecular interactions. This better cooperativity is due to a significant increase of the number of contacts between the various moieties within the (Cp2∗Mn)[Ni(dmid)2]·solvent. On the contrary, the inclusion of larger solvents such as benzonitrile in this type of complexes results in a totally different structural arrangement, which leads to an antiferromagnetic behaviour for 3.

The synthesis, X-ray and electronic structures of electroconducting radical ion salts based on organic donors (BETS and EDX-DMTTF (X=O, Se)) with inorganic counter-ions having photochromic properties are reported.

The physical properties of BETS (=bis(ethylenedithio)tetraselenafulvalene) conductors with tetrahalide magnetic anions and related systems were investigated. We have recently succeeded to find the superconducting transition of the crystal of κ-type TlCl4− salt coated with epoxy resin (Tc(onset)=2.5 K). The specific heat measurements on the antiferromagnetic organic superconductor, κ-(BETS)2FeCl4 was performed down to 60 mK, which gave sharp peak at 0.45 K (TN). The peak trails a tail at T>TN, suggesting low-dimensionality of the spin system. Resistivity measurements under magnetic field of λ-(BETS)2FexGa1−xCl4 (x≈0.4) exhibiting superconductor-to-insulating (SC–I) transition, I–SC phase transition was observed around 4 T at T<3 K. The “low-field superconducting region” between metallic and insulating phases around zero magnetic field is connected with the “high-field superconducting region”.

室温下, 用Cp2ZrCl2 与LiC≡CPh反应, 合成了碳碳偶合反应的Zr(Ⅱ)阴离子中间体Li[Cp2Zr(C≡CPh)(η2:1,2-PhC2C≡CPh)]. 用元素分析、核磁共振谱和红外光谱对配合物进行了表征, 配合物的晶体结构分析给出了两个炔烃之间碳碳偶合的证据. 用核磁共振谱初步探讨了合成反应机理.

The synthesis and characterisation (X-ray structure and magnetism) of metal complexes (Ni, An) with the [Mn(Cp*)(2)](+) cation and the dmit(2-) and dmid(2-) ligands are reported. [Mn(Cp-.)(2)][Ni(dmit)(2)] (1) and [Mn(Cp-.)(2)][Au(dmit)(2)] (2) exhibit the same structural arrangement, built on stacks of [Ni(dmit)(2)](-) pairs separated by two [Mn(Cp-.)(2)](+) cations, showing a ...D(+)D(+)A(-)A(-)D(+)D(+)A(-)A(-)... motif. On the contrary, the druid(2-) derivative [Mn(Cp-.)(2)][Ni(dmid)(2)].CH3CN (3) exhibits a totally different structure, built on mixed layers composed of one [Ni(dmid)(2)](-) unit separated by two [Mn(Cp-.)(2)](+) cations, showing a ...D(+)D(+)A(-)D(+)D(+)A(-)...motif. The layers are separated from each other by perpendicular [Ni(dmid)(2)](-) units and solvent molecules. Compound 2 exhibits antiferromagnetic interactions, whereas 1 and 3 exhibit ferromagnetic interactions at low temperature. Moreover, as confirmed by AC and DC magnetic susceptibility measurements, 1 is a ferrimagnet, the first ever derived from a 1,2-bis-dithiolene ligand. The ferromagnetic interactions in 1 and 3 are explained using the McConnell I mechanism. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

A new family of nickel ethylenetetrathiolate polymers with metallocenium cations has been prepared. Structural informations about these amorphous polymers have been determined by wide angle X-ray scattering. The magnetic properties of these polymer salts has been studied by SQUID measurements.

Radical-cation salts of iodine-substituted TTF derivatives [diiodoethylenedithiotetrathiafulvalene (1) diiodoethylenedithiodiselenadithiafulvalene (2), or iodoethylenedithiotetrathiafulvalene (3)] with the [Fe(CN)(5)NO](2-) nitroprusside anion, namely, 1(4)(.)[Fe(CN)(5)NO], 2(4)(.)[Fe(CN)(5)NO] and 3(3)(.)[Fe(CN)(5)NO], were synthesized by electrocrystallization from solutions of the appropriate TTF derivative in CH2Cl2 with bis(tetraphenylphosphonium)nitroprusside [(PPh4)(2)(Fe(CN)(5)NO)] as electrolyte. An X-ray structure analysis indicates that the crystal structures of 1(4)(.)[Fe(CN)(5)NO] and 2(4)(.)[Fe(CN)(5)NO] are very similar. In both cases, molecules 1 and 2 are stacked along the c direction, with their long molecular axis parallel to each other. By contrast, in 3(3)(.)[Fe(CN)(5)NO], molecules 3 are stacked in triad units in which two of the molecules are arranged in a face-to-face fashion and the remaining molecule is arranged in a head-to-tail fashion with respect to its neighboring molecules. In all cases, several effective iodine-nitrogen contacts between donor molecules and [Fe(CN)(5)NO](2-) anions are observed. The room temperature electrical conductivities of 1(4)(.)[Fe(CN)(5)NO], 2(4)(.)[Fe(CN)(5)NO] and 3(3)(.)[Fe(CN)(5)NO] are <10(-6), 2.2 x 10(-2) and 5 S cm(-1), respectively. The temperature dependence of the electrical conductivity of 3(3)(.)[Fe(CN)(5)NO] reveals semiconducting behavior with a small activation energy of 30 meV The temperature dependence of the electrical conductivity of 2(4)(.)[Fe(CN)(5)NO] also reveals a semiconducting behavior, but with two regimes: above 200 K the activation energy is 60 meV and becomes much smaller -0.2 meV - below this temperature. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).

室温下, [Cp2Ti(C≡CPh)2], [Cp2Zr(C≡CPh)2]和[(C5H4SiMe3)2Zr(C≡CPh)2]分别与二茂钒作用, 合成了[Cp2V(μ-η2∶η4-PhC4Ph)MCp2′] (1, M=Ti, Cp′=C5H5; 2, M=Zr, Cp′=C5H5; 3, M=Zr, Cp′=C5H4SiMe3). 用元素分析、质谱、核磁共振谱、磁矩、红外和拉曼光谱对配合物进行了表征. 3个配合物具有相似的磁化率, 配合物3的晶体结构分析表明PhC4Ph通过内部2个碳原子键合到Cp2V上, 内部2个碳原子和外部2个碳原子均与Cp2′Zr键合, 丁二烯骨架内部的2个碳原子都具有四配位的平面结构.

The reaction of [CP2Ti(Cequivalent toCPh)(2)], [Cp2Zr(Cequivalent toCPh)(2)], [(C5H4SiMe3)(2)Zr(Cequivalent toCPh)(2)] and vanadocene in toluene was performed at room temperature and gave heterodimetallic complexes [Cp2V(mu-eta(2) : eta(4)-PhC4Ph) . MCp2'] (1, M=Ti, Cp'=C5H5; 2, M Zr, Cp' =C5H5; 3, M=Zr, Cp' C5H4SiMe3), respectively. These compounds, which have been characterized by elemental analysis mass spectrometry, H-1 NMR, IR and Raman spectroscopy, exhibit similar magnetic susceptibilities. According to an X-ray diffraction analysis of compound 3, the Cp2V and CP2'Zr metallocene moieties are bonded to a butadiene(or butadiyne) framework via the two internal carbon atoms for Cp2V, and via both the two internal carbon atoms and the two external carbon atoms for CP2'Zr. The distances and angles observed around the internal carbon atoms of the butadiene framework indicate that both internal carbon atoms of butadiene skeleton are planar and tetracoordinated.

Among six BETS (=bis (ethylenedithio)tetraselenaful valene) superconductors, the systems with FeX4-(X=Cl, Br) anions exhibit salient electronic properties due to the coupling between pi and d electron systems. lambda-BETS2FeCl4 undergoes successive transitions as, antiferromagnetic insulating phase --> metallic phase with ferromagnetically oriented Fe3+ spins --> superconducting phase (H//conduction plane) --> metallic phase, with increasing magnetic field. kappa-BETS2FeX4. exhibits successive anti ferromagnetic and superconducting transitions with decreasing temperature. Resistivity anomaly observed at anti ferromagnetic transition temperature indicates an evidence for the Coupling between pi and d electron systems.

Chemical Vapor DepositionVolume 8, Issue 4 p. 145-147 Communication A New Chromium-Based Molecular Magnet Grown as a Thin Film by CVD H. Casellas, H. Casellas Laboratoire de Chimie de Coordination du CNRS, UPR 8241, 205, Route de Narbonne, F-31077 Toulouse Cedex 4 (France)Search for more papers by this authorD. de Caro, D. de CaroSearch for more papers by this authorL. Valade, L. Valade Laboratoire de Chimie de Coordination du CNRS, UPR 8241, 205, Route de Narbonne, F-31077 Toulouse Cedex 4 (France)Search for more papers by this authorP. Cassoux, P. Cassoux Laboratoire de Chimie de Coordination du CNRS, UPR 8241, 205, Route de Narbonne, F-31077 Toulouse Cedex 4 (France)Search for more papers by this author H. Casellas, H. Casellas Laboratoire de Chimie de Coordination du CNRS, UPR 8241, 205, Route de Narbonne, F-31077 Toulouse Cedex 4 (France)Search for more papers by this authorD. de Caro, D. de CaroSearch for more papers by this authorL. Valade, L. Valade Laboratoire de Chimie de Coordination du CNRS, UPR 8241, 205, Route de Narbonne, F-31077 Toulouse Cedex 4 (France)Search for more papers by this authorP. Cassoux, P. Cassoux Laboratoire de Chimie de Coordination du CNRS, UPR 8241, 205, Route de Narbonne, F-31077 Toulouse Cedex 4 (France)Search for more papers by this author First published: 02 July 2002 https://doi.org/10.1002/1521-3862(20020704)8:4<145::AID-CVDE145>3.0.CO;2-VCitations: 15AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat Abstract The feasibility of depositing thin molecular magnet filmsusing CVD is demonstrated. Two types of thin films Cr(TCNE)x (TCNE = tetracyanoethylene) and [Cr(C6H6)2][TCNE] are grown on KBr substrates at low pressure. Magnetic measurements of Cr(TCNE)x, which is air-stable, indicate that the film is magnetically ordered at 5 K with SEMs showing evidence of agglomerated micrograins 0.5–2 μm in size. X-ray photoelectron analyses and infrared spectra confirm the presence of a monoreduced TCNE moiety. [Cr(C6H6)2][TCNE] is found to be unstable even under an argon atmosphere. Citing Literature Volume8, Issue4July, 2002Pages 145-147 RelatedInformation

Owing to the coupling between π and d electron systems, organic conductors based on BETS molecules and magnetic anions such as FeCl4− and FeBr4− exhibit very unique physical properties. The orthorhombic κ-(BETS)2FeBr4 system is the first antiferromagnetic organic superconductor. Due to the metamagnetic nature of Fe spin system, the magnetic field dependence of resistivity shows a strong anisotropy in the ac conduction plane below Tc. On the other hand, the triclinic modification, λ-(BETS)2FeCl4 undergoes coupled antiferromagnetic and metal–insulator (MI) transitions at 8.5K. The easy axis of the antiferromagnetic spin structure was found to be deviated from the c axis (∥ needle axis of the crystal) by 30–35°. The field-induced insulator-to-metal transition and pressure-induced superconducting transition of λ-(BETS)2FeCl4 were briefly described from the viewpoint of the role of coupling between π and d electron systems.

The structure of bis[4,5-ethylenedithio-2-(4,5-ethylenedithio-1,3-diselenacyclopent-4-en-2-ylidene)-1,3-diselenacyclopent-4-enium] bis(mu-1,2,5-thiadiazole-3,4-dithiolato-kappa(3)S(4),S-5:S-4)bis-[(1,2,5-thiadiazole-3,4-dithiolato-kappa(2)S(4),S-5)iron(III)], (BETS)(2)-[Fe(tdas)(2)](2) [BETS is alternatively called bis(ethylenedithio)-tetraselenafulvalenium] or (C10H8S4Se4)(2)[{Fe(C2N2S3)(2)}(2)], consists of segregated columns of dimers of BETS and columns of dimers of [Fe(tdas)2]. Each dimer displays inversion symmetry. Numerous chalcogen-chalcogen contacts are observed within and between the columns, producing a network of interactions responsible for the metal-like behaviour of the compound.

The reaction of [Cp2Ti(C dropCPh)(2)], [Cp2Zr(C drop CPh)(2)] with vanadocene in toluene at room temperature gives heterodimetallic complexes [Cp2V(mu-eta(2) : eta(4)-butadiyne)MCp2] 1 (M = Ti), 2 (M = Zr), respectively. These compounds, which have been characterized by elemental analysis, mass spectrometry, IR and Raman spectroscopy, exhibit similar magnetic susceptibilities. According to an X-ray diffraction analysis of 2, the Cp2V and Cp2Zr metallocene moieties are bonded to a butadiene (or butadiyne) framework via the two internal carbon atoms for Cp2V, and via both the two internal carbon atoms and the two external carbon atoms for Cp2Zr. The distances and angles observed around the internal carbon atoms of the butadiene framework indicate that both internal carbon atoms of butadiene skeleton are planar and tetracoordinated.

Crystals of BETS conductors containing FeX4- (X = Cl, Br) anions are polymorphic lambda-BETS2FeCl4 undergoes alpha pi-d coupled antiferromagnetic insulating transition at about 8.5 K. But it exhibits a paramagnetic metal - antiferromagnetic metal transition and superconducting transition at high pressure. kappa-BETS2FeX4 (X = Cl, Br) are antiferromagnetic organic superconductors with the transition temperatures of T-N 2.4 K (Br), 0.45 K (Cl) and T-c = 1.1 K (Br) and 0.1 K(Cl). Resistivity step observed at T-N is the first direct evidence for pi-d interaction in organic metals. No distinct anomaly in the specific heat at T-c and the anisotropy of the recovery of resistivity under magnetic field at T < T-c suggest the coexistence of superconductivity and magnetic order in lambda-BETS2. FeBr4. In contrast to the case of kappa-BETS2FeBr4 exhibiting three-dimensional magnetic transition, small entropy of the transition of kappa-BETS(2)FeC1(4) indicates the low-dimensionality of the spin system.

Nanowires of tetrathiafulvalene (TTF)[Ni(dmit)2]2 (dmit2−: 2-thioxo-1,3-dithiole-4,5-dithiolato) are obtained by successively dipping SSCC in acetonitrile solutions of (Bu4N)[Ni(dmit)2] and (TTF)3(BF4)2, observed by S.E.M. and AFM, and characterized by Raman micro-probe. Thin films of (TTF)[Ni(dmit)2]2 are obtained by the same process but using a new original silicon conversion coating (SiCC). The deposit is observed by S.E.M., and characterized by Raman micro-probe and transport measurements. TTF·tetracyanoquino-dimethane (TCNQ) individual nanowires and (TTF)[Ni(dmit)2]2 nano-needles scattered on the surface of the substrate or aggregated in wads, are obtained by the dipping process on oxide-free micro-rough silicon (O-f.Mr.Si). Adherent thin films of the V(TCNE)2 (TCNE: tetracyanoethylene) magnet are deposited on (O-f.Mr.Si) substrates by chemical vapor deposition from bis(benzene)vanadium and TCNE as precursors.

室温下,[Cp2Ti(C=CPh)2]和[Cp2Zr(C≡CPh)2]分别与二茂钒作用,首次合成了[Cp2V(μ-η2:η4-PhC4Ph)MCP2]1(M=Ti),2(M=Zr).用元素分析、质谱、磁矩、红外和拉曼光谱对配合物进行了表征,两个配合物具有相似的磁化率,配合物2的晶体结构分析表明PhCrPh通过内部两个碳原子键合到CP2V上,内部两个碳原子和外部两个碳原子均与Cp2Zr键合,丁二烯骨架内部的两个碳原子都具有四配位的平面结构.用核磁跟踪技术初步探讨了合成反应机理.