3d and 4d coordination complexes and coordination polymers involving electroactive tetrathiafulvalene containing ligands

International audienceThe "through bond" approach has been recently developed to increase the interaction between the mobile π and localized d electrons in multifunctional molecular materials involving tetrathiafulvalene-based ligands. This article reviews the 3d and 4d coordination complexes and polymers elaborated from a library of tetrathiafulvalene derivatives containing ligands obtained recently in our group. The different synthetic ways of the complexes are highlighted as well as their chemical and physical properties

A new approach towards ferromagnetic conducting materials based on TTF-containing polynuclear complexes

International audienceFive complexes containing binuclear cation [Cu2(LH)2]2+ (LH2 = 1 : 2 Schiff base of 1,3-diaminobenzene and butanedione monoxime) were prepared and characterized. Metathesis of one perchlorate anion in [Cu2(LH)2(H2O)2](ClO4)2 (1) by anionic TTF-carboxylate (TTF-CO2−) leads to the complex [Cu2(LH)2(CH3OH)2](TTF-CO2)(ClO4)*H2O (2). Reactions of 1 with substituted pyridines bipy, dpe and TTF-CH = CH-py result in formation of the complexes {[Cu2(LH)2(bipy)](ClO4)2}n*2nH2O (3), [Cu2(LH)2(dpe)2](ClO4)2*2CH3OH (4) and [Cu2(LH)2(TTF-CH = CH-py)(H2O)](ClO4)2*1.5H2O (5), where bipy = 4,4′-bipyridine, dpe = trans-(4-pyridyl)-1,2-ethylene and TTF-CH = CH-py = 1-(2-tetrathiafulvalenyl)-2-(4-pyridyl)ethylene. Whereas complex 2 is built from discrete ionic particles (with rather long Cu-S contacts), compounds 1 and 3 contain 1D polymeric chains, in which structural units are bonded through Cu-O bonds or through bridging bipy molecule, respectively. Dinuclear complexes 4 and 5 are linked though π-stacking of dpe or TTF-CH = CH-py, respectively. All complexes are characterized by dominating ferromagnetic behavior with J values in the range from +9.92(8) cm−1 to +13.4(2) cm−1 for Hamiltonian H = -JS1S2. Magnetic properties of the compounds, containing stacks of aromatic molecules in crystal structures (4 and 5), correspond to ferromagnetic intradimer and antiferromagnetic intermolecular interactions (zJ′ = −0.158(3) and −0.290(2) cm−1, respectively). It was found that TTF-CH = CH-py ligand in [Cu2(LH)2(TTF-CH = CH-py)(H2O)]2+ could be electrochemically oxidized to cation-radical form in the solution

Redox-Active Dysprosium Single-Molecule Magnet: Spectro-Electrochemistry and Theoretical Investigations

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The Effect of Using Low-Phytate Cereal Varieties on Phosphorus Digestibility and Selected Production Indices

The pollution of surface waters by excessive biogenic elements, especially phosphorus, is a highly topical subject. Fishery management on ponds may be one of the potential sources of phosphorus in waters. Cyprinid fish generally have a very poor digestion of the phosphorus contained in the plant-based components of feeds. In them, phosphorus is deposited in the form of phytic acid which is almost indigestible for cyprinids. The conducted testing was focused on affecting the digestibility of phosphorus contained in plant-based feeds. Two of the cereals most frequently grown in the Czech Republic were tested, namely, wheat and barley. Control feeds were varieties commonly grown in our country, i.e. Vánek and Bojos. Furthermore, we used special cereal mutant lines with a decreased content of the phytic acid, JS-12/IDO 563 and M955. The test results showed that when using the low-phytate wheat line, the digestibility of phosphorus was increased by up to 11.21 % (P < 0.01); and by 5.89 % (P < 0.05) in the case of barley. Both low-phytate lines of the cereals used significantly affect phosphorus digestibility and decrease the loading of the environment with phosphorus. When using the low-phytate wheat line, a significant effect (P < 0.05) was found on the fat content in the fish body compared to the control variety but also compared to the low-phytate barley line. No significant effect was found comparing both control varieties and comparing the barley varieties mutually.O

Magnetic Slow Relaxation in a Metal–Organic Framework Made of Chains of Ferromagnetically Coupled Single-Molecule Magnets

International audienceWe report the study of a Dy-based metal-organic framework (MOF) with unprecedented magnetic properties. The compound is made of nine-coordinated Dy-III magnetic building blocks (MBBs) with poor intrinsic single-molecule magnet behavior. However, the MOF architecture constrains the MBBs in a one-dimensional structure that induces a ferromagnetic coupling between them. Overall, the material shows a magnetic slow relaxation in absence of external static field and a hysteretic behavior at 0.5K. Low-temperature magnetic studies, diamagnetic doping, and ab initio calculations highlight the crucial role played by the Dy-Dy ferromagnetic interaction. Overall, we report an original magnetic object at the frontier between single-chain magnets and single-molecule magnets that host intrachain couplings that cancel quantum tunneling between the MBBs. This compound is evidence that a bottom-up approach through MOF design can induce spontaneous organization of MBBs able to produce remarkable molecular magnetic materials

Clinical report of cervical arthroplasty in management of spondylotic myelopathy in Chinese

OBJECTIVES: To investigate clinical effects and manual operational point of Bryan cervical disc prosthesis in Chinese, to observe the stability and range of movement (ROM) post-operatively. METHODS AND MATERIALS: From 2003,12 to 2005,12, Bryan disc prosthesis replacement applied in 83 cases (102 levels) of cervical spondylotic myelopathy (CSM) after anterior decompression in our hospital. Clinical (JOA grade and Odom's scale) and radiological (X-ray of flexion, extension; left and right bending position) follow-up was performed. Systemic radiographic study about stability and ROM of replaced level post operationally were measured. CT or MRI scans were applied in all cases to evaluate the signs of the prosthesis deflexion and hetero-ossification in the replaced levels. RESULTS: At least 12 months follow-up were done in 65/83 of these paients. All of 83 patients were improved according to Odsm's scale. JOA score increased from average 8.7 to 15.5. There was no prosthesis subsidence. Replaced segment achieved stability and restored partial of normal ROM 4.73°(3.7°–5.9°) early postoperation and 8.12°(5.8°–13.6°) more than 12 months postoperation in flex and extension position. No obvious loss of lordosis was found. CT or MRI follow-up shows position deflexion of the prosthesis metal endplates (<1.5 mm) in 14/77 levels and (1.5~3 mm) in 4/77. heter-ossification was found in the replaced levels only in 2 cases. CONCLUSION: Byran cervical disc prosthesis restored motion to the level of the intact segment in flexion-extension and lateral bending in post-operative images. At the same time, it can achieve good anterior decompression treatment effect and immediate stability in replaced 1 or 2 levels, and which is a new choice for the treatment of CSM

Field-Induced Dysprosium Single-Molecule Magnet Based on a Redox-Active Fused 1,10-Phenanthroline-Tetrathiafulvalene-1,10-Phenanthroline Bridging Triad

Tetrathiafulvalene and 1,10-phenanthroline moieties present, respectively remarkable redox-active and complexation activities. In this work, we investigated the coordination reaction between the bis(1,10-phenanthro[5,6-b])tetrathiafulvalene triad (L) and the Dy(hfac)3·2H2O metallo precursor. The resulting {[Dy2(hfac)6(L)]·CH2Cl2·C6H14}3 (1) dinuclear complex showed a crystal structure in which the triad L bridged two terminal Dy(hfac)3 units and the supramolecular co-planar arrangement of the triads is driven by donor-acceptor interactions. The frequency dependence of the out-of-phase component of the magnetic susceptibility highlights three distinct maxima under a 2000 Oe static applied magnetic field, a sign that 1 displays a Single-Molecule Magnet (SMM) behavior with multiple magnetic relaxations. Ab initio calculations rationalized the Ising character of the magnetic anisotropy of the DyIII ions and showed that the main anisotropy axes are perpendicular to the co-planar arrangement of the triads. Single-crystal rotating magnetometry confirms the orientation of the main magnetic axis. Finally combining structural analysis and probability of magnetic relaxation pathways through Quantum Tunneling of the Magnetization (QTM) vs. excited states (Orbach), each DyIII center has been attributed to one of the three observed magnetic relaxation times. Such coordination compound can be considered as an ideal candidate to perform redox-magnetic switching