Gallium(III) and Indium(III) Complexes with meso-Monophosphorylated Porphyrins: Synthesis and Structure. A First Example of Dimers Formed by the Self-Assembly of meso-Porphyrinylphosphonic Acid Monoester

Abstract

The synthesis and structural characterization, both in solution by means of H andP NMR and UV-vis spectroscopies and in the solid state by X-ray diffraction on single crystal, of a series of gallium(III) and indium(III) meso-mono(diethoxyphosphoryl)porphyrins bearing different peripheral substituents as well as the corresponding monoesters and phosphonic acids are reported. This work describes the first example of the X-ray structure of a self-assembled dimer formed via strong binding between the oxygen atom of the phosphonate substituent and the gallium(III) cations of adjacent porphyrin molecules [Ga-O = 1.9708(13) Å].

Synthesis of (trans‐A2)BC‐Type Porphyrins with Acceptor Diethoxyphosphoryl and Various Donor Groups and their Assembling in the Solid State and at Interfaces

“…Surprisingly, this compound was identified by spectroscopic methods and HR‐MS as monoethyl porphyrinylphosphonate 4c . The 1 H and 31 P{ 1 H} NMR spectra of 4c are typical for meso ‐ethoxyhydroxyphosphoryl porphyrins, the P(O)(OH)(OEt) signals appear at δ H 3.84 and 1.12 and δ P 17.34 ppm The role of thiophenol in this competing reaction was not investigated but the dealkylation of dialkyl phosphonates in the presence of nucleophiles such as triethylamine or triphenylphosphane was previously reported …”

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

“…This work described the first example of the X-ray structure of a self-assembled dimer formed via strong binding between the oxygen atom of the phosphorus substituent and the gallium(III) cations of adjacent porphyrin molecules. [19] …”

“…a first example of dimers formed by the self-assembly of mesoporphyrinylphosphonic acid monoester. [19] Figure 16. Supramolecular assembly of organophosphonate diesters using paddle-wheel complexes: first examples in porphyrin series.…”

Electrochemical, Spectroelectrochemical, and Structural Studies of Mono- and Diphosphorylated Zinc Porphyrins and Their Self-Assemblies

“…[28][29][30] In particular, many new A 2 B-, A 2 BC-and trans-A 2 B 2 -type porphyrins (B = diethoxyphosphoryl) were prepared taking advantage of the relatively simple separation of the target molecules from crude mixtures of the polar porphyrin derivatives. 31 These photo-and air-stable porphyrin pigments with phosphoryl groups show promise for high-value-added applications in the area of energy production, optoelectronics, fine chemicals synthesis and health care. 26,27,[32][33][34][35][36][37][38][39][40][41][42][43] For instance, porphyrinylphosphonic acids and their monoalkyl esters have led to the preparation of water-soluble porphyrins which have been extensively investigated for use in biomedicine (e.g.…”