Electrochemical, Spectroelectrochemical, and Structural Studies of Mono- and Diphosphorylated Zinc Porphyrins and Their Self-Assemblies - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Inorganic Chemistry Année : 2019

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

Résumé

Three series of porphyrins containing a Zn(II) central metal ion and zero, one or two phosphoryl groups at the meso-positions of the macrocycle were characterized as to their electrochemical, spectroscopic and structural properties in non-aqueous media. The investigated compounds are represented as 5,15-bis(4'-R-phenyl)porphyrinatozinc, 10-(diethoxyphosphoryl)-5,15-bis(4'-R-phenyl)porphyrinatozinc and 5,15-bis(diethoxyphosphoryl)-10,20-bis(4'-R-phenyl)porphyrinatozinc, where R = OMe, Me, H or CN. Linear-free energy relationships are observed between the measured redox potentials at room temperature and the electronic nature of the substituents at the 5 and 15 meso-phenyl groups of the macrocycle. The mono-and bis-phosphoryl derivatives with two p-CNPh substituents provide electrochemical evidence for aggregation at low temperature, a greater degree of aggregation being observed in the case of 5,15-bis(diethoxyphosphoryl)-10,20-bis(4'-CN-phenyl)porphyrinatozinc(II). This compound was characterized in further detail by variable temperature 1 H and 31 P{1H} NMR spectroscopy in solution combined with single crystal X-ray analysis in the solid state. The data obtained from these measurements indicating that this porphyrin has a dimeric structure in CDCl3 at 223-323 K but forms a 2D polymeric network when it is crystalized from a CHCl3/MeOH mixture.
Fichier principal
Vignette du fichier
InorgChem_Hal.pdf (1.63 Mo) Télécharger le fichier
InorgChem_SI_HAL.pdf (3.27 Mo) Télécharger le fichier
Origine : Fichiers produits par l'(les) auteur(s)
Loading...

Dates et versions

hal-02379905 , version 1 (25-11-2019)

Identifiants

Citer

Yuanyuan Fang, Xiaoqin Jiang, Karl Kadish, Sergey E Nefedov, Gayane A Kirakosyan, et al.. Electrochemical, Spectroelectrochemical, and Structural Studies of Mono- and Diphosphorylated Zinc Porphyrins and Their Self-Assemblies. Inorganic Chemistry, 2019, 58 (7), pp.4665-4678. ⟨10.1021/acs.inorgchem.9b00268⟩. ⟨hal-02379905⟩
29 Consultations
126 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More