Syntheses And Properties Of Coordination Polymers Based On The Bridging Tetrathiafulvalene Ligands With Nitrogen Atoms

As an electron-donor molecule with dual step reversible redox behavior,Tetrathiafulvalene(TTF)is an important precursor in organic conducts.The redox activity can still be maintained by introducing the TTF moiety into the coordination polymers(CPs)or covalent-organic frameworks(COFs).The properties of metal complexs such as conduction,adsorption(breathing effect),magnetism and catalysis may change remarkably through oxidation,guest-exchange and other post-modifications.Based on this,two types of bridging TTF ligands with nitrogen atoms and corresponding metal coordination compounds were designed and synthesized in this paper,and their structure,magnetism,conduction and photo-catalysis were systematically studied.1.High symmetric structure of compounds[(CuI)2(L1)]n·4CH3CN(1)and[M(L1)Cl2]n(M=Fe,Co,Ni)(2)were synthesized successfully based on the bridging TTF(Pm)4[Tetra(pyrimindin-5-yl)-tetrathiafulvalene,Li]ligand.One-dimensional chain compound[(CuI)(L1)]n-CH3CN(la)was obtained consequently by irreversible Single Crystal to Single Crystal transformation of 1.Compound 1 was a new type of structure with zjl point symbol topologically.Single crystal data reveals 2-Fe,2-Co,2-Ni are isomorphic compounds.The results of solid electrochemical showed that both 1 and la were unstable and 2-Fe,2-Co,2-Ni were stable.2-Fe,2-Co,2-Ni exhibited typical paramagnetic behavior,respectively.2.A series of compounds{[Zn(L2)(NCN)]n(ClO4)·CHCl3-CH3OH}(3),{[M2(L2)2(NO3)2(H20)]n(NO3)2-2CHCl3}(M=Co,Zn)(4),{[MnCl2(L2)]n CHC13}(5),[Fe(L2)2(H2O)4(ClO4)2-2CH3OH](6)were synthesized successfully based on the novel bridging TTF(i-ql)4[Tetra(isoquinolin-6-yl)-tetrathiafulvalene,L2]ligand.Compound I3-@3 and TCNQ·-@3 were obtained by I2 doped oxidized and anion exchange post-modification of compound 3,respectively.Compound 4 and 5 were similar 2D layer as 4-Co and 4-Zn were isostructural frameworks.Compound 6 was a mononuclear complex of which electrical conductibility is about 10-7 S cm-1 resulted from the short distance between the TTF packing layer.Compound 4-Co,5,6 exhibited typical paramagnetic behavior,respectively.3.The first compound {[Zn(L2)(N2)1/2(TCNQ2)1/2]n·(TCNQ)1/2·CHCl3)}(Zn-MOF)with coordinated dinitrogen anion based on the L2 ligand was successfully synthesized.The photo-catalytic nitrogen fixation effect of Zn-MOF was studied.Half a TCNQ(Tetracyanoquinodimethane)radical molecule as an counterion was demonstrated by Single crystal diffraction,EPR and Static magnetic test,which did shorten the π…π distance between the TTF layers and electrical conductivity at room temperature is about 10-6 S cm-1.Furthermore,detailed analyzed with IR,Raman and EPR spectroscopy reveals the existence of dinitrogen anion in crystal lattice.Zn-MOF exhibited excellent and specific catalytic nitrogen reduction effect speed rate as high as 150 μmol g-1 h-1,which was much higher than that of other dintrogen complexes.