Diphosphine modified copper(I)-thiacalixarene supramolecular structure for effective photocurrent response and photodegradation of methylene blue

A diphosphine ligand modified copper(I)-thiacalixarene supramolecular compound, [Cu2(TC4A)(dppm)]·2H3O+·2MeCN (1), has been synthesised and is a potential semiconductor material. It has good photo-induced electron/hole pair generation, separation efficiency in an FTO electrode and can effectively degrade methylene blue. [Display omitted] In this paper, a diphosphine ligand modified copper(I)-thiacalixarene compound, [Cu2(TC4A)(dppm)]·2H3O+·2MeCN (1) (H4TC4A = p-tert-butylthiacalix[4]arene, dppm = 1, 1-bis(diphenylphosphine)methane), was obtained by the assembly of Cu(OAc)2·H2O, H4TC4A and dppm in a mixed solution of acetonitrile and dichloromethane. Compound 1 was well defined. Single crystal X-ray diffraction analysis shows the central skeleton of 1 has two copper atoms, one TC4A4− ligand and one dppm ligand. Compound 1 was characterized by 1H and 31P NMR, Fourier transform infrared (FT-IR), X-ray photoelectron (XPS), ultraviolet–visible (UV–Vis) absorption and diffuse reflection spectra, together with thermogravimetric (TG) analysis. Furthermore, the luminescence, photocurrent response characteristic, photocatalytic performance and electrochemistry of 1 have been investigated. Compound 1 has better photo-induced electron/hole pair generation and separation efficiency in an FTO electrode. The degradation rate of methylene blue (MB) with the addition of 1 was approximately 88%, which was significantly higher than that without the catalyst within 300 min. These results indicate that compound 1 has good light-emitting and photoelectric properties and will be a potential semiconductor material.