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 complexes Author: Wang Yu Degree-granting units: Northeast Normal University Keywords: Four thiosulfate Foix en;; π-d interaction;; complexes;; crystal structure;; phase transition;; water cluster Abstract: Dual-function materials for Neodymium Magnets electromagnetic research is the synthesis and materials chemistry research focus, the origin of the field to the initial
Back for the four thio-Foix ene (TTF) of the 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
Battery and nonlinear optical materials are widely used, the most active research to multifunctional molecule-based materials are synthesized. Design
Both electrical conductivity and a magnetic molecules (materials) particularly attractive to a lot of interest in chemistry and physics. To achieve this goal
Way in organic π-electron donor and the localized d electrons of the paramagnetic ion coupling established between the π-d interaction, and achieve the π-d interaction
Can usually be used two ways: (a) the interaction through space to achieve π-d interaction, but such interactions will be relatively weak;
(B) the two systems connected by chemical bonds, so as to effectively achieve the π-d interaction. To design each with a strong π-d
Dual role of functional materials, we have successfully synthesized four groups with coordination of the novel TTF derivatives. And using 1 - (4 -
(Tetrathiafulvaleneyl) phenyl) ethanone (TTF-PEO) and 1 - (4-tetrathiafulvalyphenyl) -4,4,4 -
trifluorobutane-1 ,3-dione (TTF-ph-tfacH) were prepared by a solvent-dependent CuBr_42? charge-transfer salts and metals
MII (M = Zn, Co) complexes. This will be the integration of new molecular-based magnetic materials to provide theoretical http://www.everbeenmagnet.com/en/products/110-sintered-neodymium-magnets and experimental basis. Research work
Includes the following four parts: 1, synthesized as a precursor of electromagnetic integration of the four materials in novel TTF derivatives, and through
Through mass spectrometry, infrared, ultraviolet 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) were replaced with single-triazole, terpyridine, benzene
Ethyl ketone and β-diketone ligand groups. The four compounds tested successfully CV step oxidation of TTF radical cation and two
Cation, showing the reversible one-electron oxidation process. Their electrochemical behavior is similar to the parent TTF, so they can be used as
Good for the body material is widely used. While each single compound are replaced by asymmetric molecules, such compounds in non-
Linear optical materials may have potential applications in the field. 2, by changing the solvent to achieve a convenient way to adjust the TTF-PEO's
Charge transfer for the +1 and +2, respectively, synthesized compounds (TTF-PEO) _2CuBr_4 (5) and (TTF-PEO) _2 (CuBr_4) _2 ·
CH_2Cl_2 · CH_3CN (6), crystal structure analysis shows that they belong to the Pī triclinic and orthogonal space group Pbca. Containing a single to take
Substituent of the TTF-PEO will help to significantly reduce the organic donor and the distance between the paramagnetic ion, 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
There may be a strong π-d interaction. With anti-ferromagnetic behavior of compound 5 in the 110-120K observed phase transition occurs, is
These compounds have been reported in the highest phase transition temperature. 3, TTF-ph-tfac enol anion has a strong coordination ability, and
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 ligand. Electrochemical behavior of the test indicates that the
Dual-function electromagnetic system can be used as precursor materials. 8 shows the magnetic test between the central metal is weak antiferromagnetic interaction.
4, synthesized 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, the phthalate anion
Sub-bridged CuII center to form a Z-infinite chain. Exist in 10 (H_2O) 16 and (H_2O) 10 water cluster containing the formation of a 2D
Water layer. Near a plane through hydrogen bonds formed by the S-and Z-water chain, respectively, 11 and 12 in the crystal structure observed. 12
In, Cu (II) center is six-coordinated, which is coordinated with the five 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 molecules occur in situ reaction terpyOH by comparison
The crystal structure of these compounds can be found, when the molecules through hydrogen bonding with terpyOH to build clusters of water molecules when the control system
deprotonation pH values ​​it will be very beneficial. Degree Year: 2009