A Solvent-Free Covalent Organic Framework Single-Ion Conductor Based on Ion-Dipole Interaction for All-Solid-State Lithium Organic Batteries

Single-ion conductors based on covalent organic frameworks(COFs)have garnered attention as a potential alternative to currently prevalent inorganic ion conductors owing to their structural uniqueness and chemical versatility.However,the sluggish Li+conduction has hindered their practical applications.Here,we present a class of solvent-free COF single-ion conductors(Li-COF@P)based on weak ion-dipole interaction as opposed to traditional strong ion-ion interaction.The ion(Li+from the COF)-dipole(oxygen from poly(ethylene glycol)diacrylate embedded in the COF pores)interaction in the Li-COF@P promotes ion dissociation and Li+migration via directional ionic channels.Driven by this single-ion transport behavior,the Li-COF@P enables reversible Li plating/stripping on Li-metal electrodes and stable cycling performance(88.3%after 2000 cycles)in organic batteries(Li metal anode||5,5’-dimethyl-2,2’-bis-p-benzoquinone(Me2BBQ)cathode)under ambient operating conditions,highlighting the electrochemical viability of the Li-COF@P for all-solid-state organic batteries.

Synthesis of Novel Covalent-linked Linear Porphyrin-Thiophene Copolymers

Linear porphyrin-thiophene copolymers were synthesized by linking 5, 15-positions of porphyrin with tetrathiophene or bithiophene moieties for preparing conducting polymer. 2,8,12,18-tetraethyl-3,7,13,17-tetramethyl-5, 15-dithienylporphyrin4a (45.1%), 5, 15-di-bithienyl- 2,8,12,18-tetraethyl-3, 7, 13, 17-tetramethylporphyrin4b (61. 2%) and their metal complexes were also reported in high yields (>90%) as the monomers. 5, 15-di-bithienylporphyrin and its metal complexes could be polymerized by oxidation using FeCl3 as oxidant. However, 5,15-dithienylporphyrin and its metal complexes can not be polymerized by same reaction. Their polymers were synthesized by electrochemical oxidation on the gold-plate electrode. The structures of copolymers were identified by elemental analysis and IR spectra. And the conductivity of poly 5,15-di-bithienylporphyrin was measured to reach over 1.0× 10?6S/cm. Key words organic conductor - thienylporphyrin - porphyrin-thiophene copolymer - electropolymerization CLC number O 62 Foundation item: Supported by the National Natural Science Foundation of China (29872033, 20272046)Biography: CHEN Zhang-ping (1946-), male, Professor, research direction: porphyrin chemistry.

Preparation and Properties of(BEDT-TTF)_2Br3H_2O Salt

Electrochemical oxidation of BEDT-TTF (bis (ethylenedithio) tetrathiafulvalene) inchloroform/carbon disulfide (3:1) in the presence of Bu4NBr as a supporting electrolyte at lowcurrent density results in the (BEDT-TTF)2Br3H2O crystal. Its composition has been established bychemical analysis (Br, C, H, S), XPS and IR. The temperature dependence of the resistance has beenstudied down to 26K at ambient pressure. This material has weakly metallic behavior above 230K,and becomes a semiconductor below this temperature. The structure of the complex is alsodescribed.

Synthesis of Covalently-linked Linear Donor-Acceptor Copolymers Containing Porphyrins and Oligothiophenes

A series of monomers of 5,15-dithienyl porphyrin, 5,15-di-bithienyl porpyrin and their metal complexes were synthesized in high yields. 5,15-Di-bithienyl porphyrin and its metal complexes were polymerized by chemical oxidation using FeCl3 as oxidant (>90%) for making organic conductor and the linear porphyrin-thiophene co- polymers were obtained. The structures of the copolymers were identified by elemental analysis and IR spectra. The conductivity of poly 5,15-di-bithienyl porphyrin was measured to reach over 10-6 S/cm. 5,15-Dithienyl porphyrins and its metal complexes could not be polymerized under the similar conditions, but could be polymerized by elec- trochemical oxidation on the gold-plate electrode.