Syntheses And Properties Of Carboxylic Groups-containing Resorcin[4]arene-based Complexes

Two carboxylic groups-containing resorcin[4]arene derivatives have been designed and synthesized.We have obtained six complexes with novel structures and potential applications through the reaction with different metal ions.Their crystal structures were determined by single crystal X-ray diffraction（SC-XRD）.The complexes were characterized by XRD,XPS,EDS,TEM,IR,Raman,UV,TGA and ESI-MS.The complexes have been used in the study of catalytic oxidation of H₂O,conducting switch of NO₂ and cycloaddition of CO₂ with epoxides.1.We have successfully designed a new metal-organic supramolecular complex1 by using resorcin[4]arene ligand and Cu（II）cation.It is the first time that resorcin[4]arene-based complex is used in the bismuth vanadate（BVO）photoanode for the OER reaction,which is about three times as high as that of BVO photoanode.Photoelectrochemical and electrochemical analysis showed that the film of 1displayed the dual functions of hole layer and catalyst layer,which inhibited the recombination of photogenerated carriers and promoted the OER efficiency.This work provides a new strategy for the construction of efficient photoanodes by using resorcin[4]arene-based complexes.2.A cobalt coordinated resorcin[4]arene compound 2 was successfully synthesized by a solvothermal reaction.The conductivity of 2 is increased by 6million times after adsorption of NO₂.The reversible conductivity switch is controlled by NO₂ adsorption and desorption.Heated 2 to get 3（After lost of free water）,the maximum NO₂absorption of 2 and 3 were 4.9 and 6.5 mmol g^-1（298 K,1 bar）,respectively.This work provides direct experimental evidence for the adsorption of NO₂ by MOF.It reveals the further development of gas responsive conductive MOF materials.3.A cadmium-coordinated resorcin[4]arene MOF 5 have been successfully synthesized through a solvothermal reaction.When MOF 5 was added to the Cu（II）solutions,the cadmium ion in MOF 5 was partially replaced by Cu（II）to form a new metal-mixed MOF 6.Due to the Jahn-Teller effect,Cu atom shows a four coordinated planar square structure with four O atoms,which provides more catalytic sites for the cycloaddition of carbon dioxide with epoxides.We find that the catalytic effect of the substituted by Cu（II）ion is significantly better than that of 5.