Synthesis, Characterization, and Electronic Properties of Metalloporphyrins Annulated to Exocyclic Imidazole and Imidazolium Rings

Abstract

Abstractmeso‐Tetraarylporphyrin complexes (M = Ni, Cu, Zn, H2) fused to an imidazole ring across two neighboring β‐pyrrolic positions were synthesized through a cyclization reaction between β,β′‐diaminoporphyrins and formic acid or trimethyl orthoformate under acidic conditions. Two synthetic procedures were used to obtain the corresponding porphyrin N,N′‐dimethylimidazolium salts derivatives: alkylation of the imidazole nitrogen atoms with iodomethane and the cyclization reaction between the porphyrin bearing two neighboring β‐N‐methyl groups and trimethyl orthoformate in the presence of ammonium hexafluorophosphate. The electrochemical properties of these porphyrins annulated to an imidazole/imidazolium ring have been investigated by cyclic and rotating disk voltammetry.

Porphyrins Conjugated with Peripheral Thiolato Gold(I) Complexes for Enhanced Photodynamic Therapy

“…If this reaction worked well with metalloporphyrins, it failed with free base derivative Fb‐I , presumably because Ag I could be trapped by the porphyrin core. Therefore, we used another strategy to obtain [FbAuCl] in good yield starting from Zn‐I as NHC precursor (Scheme ) . First, the complex [ZnAuCl] was obtained in 71 % yield by reacting Zn‐I with Ag 2 O and transmetallating the intermediate NHC‐Ag I complex with [AuCl(tht)].…”

Unexpected Drastic Decrease in the Excited‐State Electronic Communication between Porphyrin Chromophores Covalently Linked by a Palladium(II) Bridge

“…Imidazolium salts [M] (M=Zn and Fb) were obtained in good yields starting from the meso ‐tetra(4‐ tert ‐butylphenyl)porphyrin (Scheme ) 5. The mononuclear trans ‐Pd II complex [Fb‐Fb] was selectively obtained in 58 % yield by using an excess of the imidazolium salt [Fb] (3.4 equiv) compared to the starting material Pd(OAc) 2 .…”

Multiple Linear Regression Solvatochromic Analysis of Donar-Acceptor Imidazole Derivatives

“…Polysubstituted imidazole derivatives have been used as highly sensitive fluorescent chemosensor for sensing, imaging metal ions and play an vital role in material science due to their optoelectronic properties [1][2][3][4]. Its chelates with Ir 3+ are major components for organic light emitting diodes [5].…”