Gallium(III) Corrole Complexes as Near‐Infrared Emitter – Synthesis, Computational and Photophysical Study

Abstract

We report on the chemical synthesis and characterization of free‐base A2B‐ and A3‐meso‐TIPS ethynyl corroles, which serve as a precursor for metalation with gallium(III)chloride and subsequent in‐situ sila Sonogashira cross‐coupling reaction. Under ambient conditions and with a common catalyst system the reaction with different aryliodides proved to be successful. Compared to the well‐known Ga(III)‐pyr‐5,10,15‐trispentafluorophenylcorrole complex, the emission wavelengths of such gallium(III) corroles complexes could be shifted bathochromically by up to ∼3100 cm−1 to the near‐infrared region (NIR). The described synthetic procedure establishes a facile way to obtain organic near‐infrared‐emitters based on gallium(III) meso‐aryl‐ethynyl corrole complexes.

Direct Conjugation of Gallium‐(III)‐Corroles to Short Interfering RNA(siRNA) Providing Real‐Time siRNA Imaging and Gene Silencing

“…Based on prior literature, Ga‐(III)‐corroles can behave as photosensitizers and fluorophores simultaneously [16,19] . As previously noted, corrole molecules can change its photophysical properties and its energy transfer pattern based on the modification and mode of conjugation [8a,20] . Conjugations such as electron donating groups or electron withdrawing groups can affect the photophysical properties of corrole molecules.…”

“…The literature data suggests that the presence of the hydroxyl group may have an effect on increasing the oxidation activity [17] . Although this alkynyl linker is not directly bonded to the corrole core it might still be interfering with electron density distribution of the ring and participating in energy transfer activities, thus resulting in reduced potency [8a] . However, despite the difference in the level of the cytotoxicity of the two Ga‐(III)‐corrole ligands 4 and 13 , the small molecules showed increased photodynamic effect with the addition of the Ga (III) metal.…”

Gallium (III) Complexes in Cancer Chemotherapy

“…Planar tetradentate ligands represented by porphyrin and corrole are two groups of chromophore ligands with interesting optical properties, allows their complexes as the probes of biological imaging as well as therapeutic agents [83–84] . Ga(III) complexes of porphyrin and corrole also show great antineoplastic activity in both chemotherapy and photodynamic therapy [85–86] . A series of halogenated Ga(III) corroles (Figure 4, 21 ) not only interact with DNA, but also display high photodynamic antitumor activity [87] .…”

“…[83][84] Ga(III) complexes of porphyrin and corrole also show great antineoplastic activity in both chemotherapy and photodynamic therapy. [85][86] A series of halogenated Ga(III) corroles (Figure 4, 21) not only interact with DNA, but also display high photodynamic antitumor activity. [87] Ga(III) corrole 1-Ga (Figure 4, 22) inhibited the proliferation of breast (MDA-MB-231), melanoma (SK-MEL-28), and ovarian (OVCAR-3) cancer cells primarily by arrest of DNA replication and induced late M phase arrest.…”

Oxido-Molybdenum(V) Corroles as Robust Catalysts for Oxidative Bromination and Selective Epoxidation Reactions in Aqueous Media under Mild Conditions

“…Corroles are a pivotal class of trianionic ligands that generate stable metallocorroles with a range of metal ions in formally high oxidation states. − Metallocorroles are diverse in terms of structural and redox properties and exhibit enhanced chemical as well as thermal stability along with strong absorption in the visible spectral range. − Metallocorroles are very useful in dye-sensitized solar cells, , catalysis, PDT, , chemical sensors, , and nonlinear optics , because of their customizable excitation and emission spectral features. − …”