Electromagnetic bifunctional precursor - four thio Foix ene Derivatives and Their Preparation and Characterization of Complexes

Title: Electromagnetic bifunctional precursor - four thio Foix ene Derivatives and Their Preparation and Characterization of ComplexesAuthor: Wang YuDegree-granting units: Northeast Normal UniversityKeywords: four phosphorothioate Foix ene;; π-d interaction;; complexes;; crystal structure;; phase transition;; water clustersSummary:


 Dual-function materials for electromagnetic research is the synthesis and materials chemistry research focus, the field was originally dates back to the four Magnetic lifter thio Foix ene (TTF) study. From the discovery of the first organic metal (TTF) (TCNQ) has been, TTF derivatives have been not only can be used as building blocks of organic conductors, but also in molecular machines, organic magnets, organic field-effect transistors, solar cells and nonlinear optics materials are widely used, the most active research is a synthesis of multifunctional molecules to the base material. Design a both conductive and magnetic properties of molecules (materials) particularly attractive to a lot of interest in chemistry and physics. Way to achieve this goal in organic π-electron donor and the localized d electrons of the paramagnetic ion coupling between the π-d interaction to establish, and achieve the π-d interaction can usually be used two ways: (a) through space interaction to achieve the π-d interaction, but such interaction will be relatively weak; (b) the two systems connected by chemical bonds, so as to effectively achieve the π-d interaction.


 In order to design a strong π-d interaction of dual functional materials, we have successfully synthesized four groups with a novel ligand TTF derivatives. And http://www.999magnet.com/products/131-magnetic-lifter using 1 - (4 - (tetrathiafulvaleneyl) phenyl) ethanone (TTF-PEO) and 1 - (4-tetrathiafulvalyphenyl) -4,4,4-trifluorobutane-1 ,3-dione (TTF-ph-tfacH) were prepared solvent dependent CuBr_42? charge-transfer salts and metals MII (M = Zn, Co) complexes. This will be the integration of new molecule-based magnetic materials to provide theoretical and experimental basis. Research include the following four parts:


 1, synthesized as a precursor of electromagnetic integration of the four materials in novel TTF derivatives, and by mass spectrometry, infrared, UV and NMR structural characterization. In which N-(tetrathiafulvalen-4-ylmethylene) -1,2,4-triazol-4-amine (1), 4'-tetrathiafulvaleneyl-2,2 ': 6', 2 "-terpyridine (2), 1 - ( 4 - (tetrathiafulvaleneyl) phenyl) ethanone (TTF-PEO) (3) and 1 - (4-tetrathiafulvalyphenyl) -4,4,4-trifluorobutane-1 ,3-dione (TTF-ph-tfacH) (4), respectively, with replaced by a single triazole, terpyridine, acetophenone, and β-diketone ligand groups. The cyclic voltammetry of these four compounds tested successfully for the TTF radical cation oxidation step and two-cation, show a reversible one-electron oxidation process. their electrochemical behavior is similar to the parent TTF, so they can be used as a good donor material is widely used, while each mono-substituted compounds are asymmetric molecules, such compounds In the field of nonlinear optical materials may have potential applications.


 2, by changing the solvent method conveniently adjust the TTF-PEO to achieve the charge transfer of +1 and +2, respectively, synthesized compounds (TTF-PEO) _2CuBr_4 (5) and (TTF-PEO) _2 (CuBr_4) _2 · CH_2Cl_2 · CH_3CN (6), the crystal structure analysis shows that they belong to the Pī triclinic and orthogonal space group Pbca. Containing a single substituent TTF-PEO help to significantly reduce the organic donor and paramagnetic ions, the distance, which is reflected in the 5 has the shortest Br · · · S distance, indicating that the TTF-PEO + · electron donor and CuII ions by Br · · · S · · · Br · · · S super-exchange interaction may exist strong π-d interaction. With antiferromagnetic behavior of compound 5 in the 110-120K observed the occurrence of phase transition is of such compounds has been reported the highest phase transition temperature.


 3, TTF-ph-tfac enolate anion with strong coordination ability with metal chlorides (Zn and Co) were generated chelating ligand complexes Zn (TTF-ph-tfac) _2 (CH_3OH) _2 ( 7) and Co (TTF-ph-tfac) _2 (CH_3OH) _2 (8), each center are bridging two metal TTF-ph-tfac ligands. Electrochemical behavior of the test indicates that the system can be used as dual-function electromagnetic precursor materials. 8 shows the magnetic test between the metal center is weak antiferromagnetic interaction.


 4, synthesis by single crystal X-ray diffraction characterization of four novel compounds of copper, one-dimensional chain compound {[Cu (terpyOH) (phth)] · H_2O} _n (9), dual-core compounds [Cu2 (terpyO) _2 (phth) (H_2O) _2] · 11H_2O (10), mononuclear compound [Cu (terpyOH) (SO4) (H_2O)] · 2H_2O (11) and [Cu (terpyOH) _2] · (HBTC) · 2H_2O (12 ) (terpyOH = 4'-hydroxy-2, 2 ': 6', 2 "- terpyridine, phth = phthalate, BTC = trimesic acid) in 9, bridging phthalate anions CuII center to form a Z-infinite chain exists in 10 (H_2O) 16 and (H_2O) 10 water clusters to form a 2D aquifer. a hydrogen bond formed by the S-type near-surface water and Z-type chain 11 and 12 respectively in the crystal structure observed in the 12, Cu (II) center is six-coordinated, which is five-coordinate compounds 9, 10 and 11 are different. and in the process of synthesis of compound 11 , found in hydrothermal conditions 4'-bromo-2, 2 ': 6', 2 "- terpyridine occurs in situ reaction terpyOH molecules. By comparing the crystal structures of these compounds can be found, when the molecules through hydrogen bonds with terpyOH to build clusters of water molecules when the pH of the control system to take off protons will be very beneficial.Degree Year: 2009