Silicon(IV) Corroles

Abstract

Silicon complexes of corrole were obtained for the first time by reaction of the free-base corrole with hexachlorodisilane. The peripheral substituents of corrole strongly influence the nature of the reaction products: β-octaalkyl corrole was mainly isolated as the μ-oxo dimer, while a hydroxo complex was obtained in the case of 5,10,15-tris-(pentafluorophenyl)corrole. In the case of meso-tritolyl corrole, a mixture of monomer/μ-oxo dimer was obtained. The silicon corrole complexes are more stable toward hydrolysis than the corresponding porphyrin derivatives and are endowed with brilliant luminescence properties. The high affinity of silicon for fluoride ion allowed investigation of the ability of an Si corrole to serve as a sensor for F detection. The strong color variation due to the interaction with the halide ion makes the Si corrole an interesting material for the naked-eye detection of inorganic fluoride.

How does tautomerization affect the excited-state dynamics of an amino acid-derivatized corrole?

“…As important as the discovery of corroles was in the 1960s (Johnson and Price 1960a , b ; Johnson and Kay 1961 , 1964 , 1965 ), it was four decades later when the first reports of the one-pot syntheses of such macrocycles drew considerable attention to these chromophores by making them readily accessible (Gryko and Jadach 2001 ; Gross et al 1999 ; Paolesse et al 2001 ). Similar to porphyrins, corroles are tetrapyrroles with one less carbon in the macrocycle, resulting in electron-rich chromophores with properties that are complementary to those of other porphyrinoids (Gryko 2002 ; Orlowski et al 2017a ; Aviv-Harel and Gross 2009 ; Ghosh 2017 ; Rabinovich et al 2011 ; Pomarico et al 2018 ; Einrem et al 2016 ). The importance of corroles for solar energy conversion, photocatalysis, photodynamic therapy and other areas of photonics is well recognized (Dogutan et al 2011 ; Mahammed and Gross 2006 ; Agadjanian et al 2009 ; Flamigni et al 2008 ; Teo et al 2017 ).…”

Corroles at work: a small macrocycle for great applications

“…122 The interactions with F À result in changes in both absorbance and fluorescence with high selectivity as compared to other anionic species. 123 Fig. 61 shows the color comparison of Si IV triarylcorrole in a DMSO/H 2 O) solution with 10 À5 M of different anions.…”

On-Surface Synthesis of Nonmetal Porphyrins

“…In a molecular setting, silicon porphyrin complexes − have gained attention because of their unique features and functions, such as a peculiar conformational structure, ,,, distinct photochemical and photocatalytic properties, and their use in dye-sensitized cells . Such silicon-porphyrin derivatives have been synthesized in solution, mostly including Si-bound axial ligands commonly yielding a Si oxidation state of +4. ,,− In addition to Si-porphyrins, Si-phthalocyanines − and Si-corroles were achieved and comprehensively characterized in view of manifold potential applications. However, the on-surface synthesis of Si tetrapyrrole complexes, and more specifically silicon porphyrins, has not been reported to date.…”

“…33 Such silicon-porphyrin derivatives have been synthesized in solution, mostly including Si-bound axial ligands commonly yielding a Si oxidation state of +4. 32,34,38−41 In addition to Si-porphyrins, Si-phthalocyanines 42−47 and Sicorroles 48 were achieved and comprehensively characterized in view of manifold potential applications. However, the onsurface synthesis of Si tetrapyrrole complexes, and more specifically silicon porphyrins, has not been reported to date.…”