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.

Survey of Synthetic Routes towards Phosphorus Substituted Porphyrins

“…It was already shown that the self assembling of these phosphoryl Zn(II) and Cu(II) porphyrins should be observed in solid state and in solution. [30][31][32]34,35] This self assembling leads to 1D and 2D networks. At last but not least, the new A 3 B type phosphorylated porphyrins should be very good precursors in order to construct efficient DSSCs and to develop photocatalysts.…”

“…Palladium-catalyzed phosphorylations both at the meso position of the porphyrin ring and at the p-bromophenyl substituents were described by Enakieva et al [30][31][32] The A 4 and A 2 B 2 porphyrin types were obtained, the A 2 B 2 type being isolated in modest to good yields depending of the reaction conditions (Scheme 16).…”

Advances in Tetrapyrrolic Chemistry over 2013-2017 of Research group Headed by Full Member of RAS A. Yu. Tsivadze: Highlights on the Occasion of his Anniversary

“…For example, in the case of copper(II) bis-meso-phosphorylated porphyrin the unusual formation of a stable 2D coordination network was observed ( Figure 15). [17] Figure 15. Unusual formation of a stable 2D copper porphyrin network.…”

“…Unusual formation of a stable 2D copper porphyrin network. [17] A novel series of one-dimensional homo-and heterometallic coordination polymers was prepared from planar and nonplanar metallo(diphosphoryl)porphyrinates and dicopper(II) tetra-pivalate paddle-wheel complex (Figure 16). In these polymers, paddle-wheel dicopper(II) units are assembled with porphyrin donors in a 1:1 ratio through axial Cu-O=P coordination.…”

IMOBILIZAÇÃO DE COMPLEXO DE RUTÊNIO CONTENDO BASE DE SCHIFF NA UNIDADE METALOORGÂNICA UiO-67

“…3 Sistemas bidimensionais são obtidos pela polimetalação de estruturas planares com propriedades multiponte como as meso-tetrapiridilporfirinas de cobre. 4 Finalmente, sistemas tridimensionais podem ser obtidos pela polimetalação de complexos baseados no tris(bipiridina)rutênio(II), [Ru(bpy) 3 ] 2+ , e sistemas poli-imínicos substituídos com grupos coordenantes. 5 As vantagens de sistemas tridimensionais estão associadas ao desenvolvimento de materiais com elevada porosidade, com poros uniformes e ordenados em escala molecular, bem como na estabilidade dessas estruturas após a remoção da maior parte das moléculas do solvente presentes nos poros desse material.…”