title: Unusual formation of a stable 2D copper porphyrin network.
abstract: Copper(II) 5,15-bis(diethoxyphosphoryl)-10,20-diphenylporphyrin was obtained and characterized by means of cyclic voltammetry, electron paramagnetic resonance, Fourier transform infrared, and UV-visible spectroscopy. Three crystalline forms were grown and studied by means of X-ray diffraction methods (single crystal and powder). The highly electron-withdrawing effect of phosphoryl groups attached directly to the porphyrin macrocycle results in a self-assembling process, with formation of a stable 2D coordination network, which is unusual for copper(II) porphyrins. The resulting 2D structure is a rare example of an assembly based on copper(II) porphyrins where the copper(II) central metal ion is six-coordinated because of a weak interaction with two phosphoryl groups of adjacent porphyrins. The other polymorph of copper(II) 5,15-bis(diethoxyphosphoryl)-10,20-diphenylporphyrin contains individual (isolated) porphyrin molecules with four-coordinated copper(II) in a distorted porphyrin core. This polymorph can be obtained only by slow diffusion of a copper acetate/methanol solution into solutions of free base 5,15-bis(diethoxyphosphoryl)-10,20-diphenylporphyrin in chloroform. It converts to the 2D structure after dissolution in chloroform followed by consecutive crystallizations, using slow diffusion of hexane. A six-coordinated copper(II) porphyrin containing two axially coordinated dioxane molecules was also obtained and characterized by X-ray diffraction crystallography. The association of copper(II) 5,15-bis(diethoxyphosphoryl)-10,20-diphenylporphyrin in solution was also studied.
authors.affiliation: Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninsky Pr. 31, Moscow 119071, Russia.
authors.forename: Anna A
authors.initials: AA
authors.lastname: Sinelshchikova
authors.forename: Sergey E
authors.initials: SE
authors.lastname: Nefedov
authors.forename: Yulia Yu
authors.initials: YY
authors.lastname: Enakieva
authors.forename: Yulia G
authors.initials: YG
authors.lastname: Gorbunova
authors.forename: Aslan Yu
authors.initials: AY
authors.lastname: Tsivadze
authors.forename: Karl M
authors.initials: KM
authors.lastname: Kadish
authors.forename: Ping
authors.initials: P
authors.lastname: Chen
authors.forename: Alla
authors.initials: A
authors.lastname: Bessmertnykh-Lemeune
authors.forename: Christine
authors.initials: C
authors.lastname: Stern
authors.forename: Roger
authors.initials: R
authors.lastname: Guilard
mesh_terms: D003300:Copper / Q000737:chemistry*; D004578:Electron Spin Resonance Spectroscopy; D008958:Models, Molecular; D010766:Phosphorylation; D011166:Porphyrins / Q000737:chemistry*
chemical_list: D011166:Porphyrins; D003300:Copper