Corroles That “Click”: Modular Synthesis of Azido- and Propargyl-Functionalized Metallocorrole Complexes and Convergent Synthesis of a Bis-corrole Scaffold

Abstract

Bis-corroles have been prepared through a convergent synthesis using a copper-catalyzed azide-alkyne cycloaddition. Synthesis of the final homo- and heterobimetallic complexes has been achieved in three to four steps from commercially available materials in good overall yield. Meso-substituted corroles functionalized with a single azido or propargyl group were used as key starting materials. (C6F5)2(p-O(CH2CCH)Ph)corroleH3 (1) and ((C6F5)2(m-CH2N3)Ph)corroleH3 (3) were metalated with copper or iron and attached by Huisgen azide-alkyne cycloaddition ("click" reaction) first to small substrates and then to each other, demonstrating a convergent synthesis of bimetallic bis-corrole molecules.

Photometric Detection of Nitric Oxide Using a Dissolved Iron(III) Corrole as a Sensitizer

“…The lowest‐energy absorption that can be identified in the experimental spectra appears around 730 nm in all solvents tested and has a weak intensity with an extinction coefficient between 2500 and 3000 m −1 cm −1 (Table ). This absorption feature has been reported for 1 and similar complexes but for many iron(III) corroles it is too weak to be observed . According to our time‐dependent (TD)‐DFT calculations, this absorption is dominated by iron d x − y →d z transitions, which possess only small oscillator strength as reflected in the stick spectrum at 776 nm (Figure ).…”

“…This absorption feature has been reported for 1 [16] and similarc omplexes [61] but for many iron(III) corroles it is too weak to be observed. [62][63][64][65] According to our time-dependent (TD)-DFT calculations, this absorption is dominated by iron dx 2 Ày 2 !dz 2 transitions, which possess only small oscillator strength as reflected in the stick spectrum at 776 nm ( Figure 3). At even lower photon energies, weaka bsorptions due to furtherd -d transitions are predictedb yT D-DFT calculations.…”

Engaging Copper(III) Corrole as an Electron Acceptor: Photoinduced Charge Separation in Zinc Porphyrin–Copper Corrole Donor–Acceptor Conjugates

“…Consequently, there already exist a few reports on donor–acceptor dyads featuring corroles as the photosensitizer/electron donor . However, application of corroles as electron acceptors has hardly been studied,, primarily owing to the lack of a corrole or metallocorrole derivative with an appropriately facile reduction potential. The exception to this generalization is provided by the recently reported copper(III) corroles that are known to undergo facile reduction from copper(III) to copper(II) .…”

“Click”-reaction: An alternative tool for new architectures of porphyrin based derivatives

“…This reaction has been applied in many tetrapyrrolic entities such as porphyrins [55], phthalocyanines [55] and more recently corroles [56,57]. Concerning the applications of click-made porphyrins many studies have been made on photodynamic therapy (PDT) [58][59][60][61], polymers [62][63][64][65], self-assembly [66][67][68], biochemistry [69][70][71][72] and materials chemistry [73][74][75][76].…”