Amphiphilic aluminium(III) and gallium(III) corroles

Abstract

The preparation and spectroscopic properties of a series of metallocorroles with polar head groups CHO and CH = C ( CN )( COOH ) are reported, as well as the X-ray crystal structure of 5,10,15-tris(pentafluorophenyl)corrolatoaluminium(III)bispyridine (triclinic space group (P-1) with unit cell parameters: a = 9.426(1) Å; b = 13.202(1) Å; c = 19.936(1) Å; α = 74.19(1)°; β = 78.47(1)°; γ = 75.75(1)°; V = 2289.57(8) Å3). Amphiphilic aluminium(III) and gallium(III) corroles exhibit electronic absorption (Soret peaks between 410 and 448 nm; Q-bands between 584 and 638 nm) and fluorescence (band maxima between 634 and 706 nm) at lower energies than their hydrophobic analogs.

Coordination chemistry of corroles with focus on main group elements

“…The crystal structure of the bis-pyridine aluminum(III) corrole 8 reveals that the metal ion is located in the plane of the corrole macrocycle and that the two axial pyridine molecules are nearly parallel to each other with a twist angle of 3.6 • [43]. Close inspection of the two pyridine molecules suggests that they bend slightly toward each other with a bending angle of 171.5 • .…”

Cellular uptake and anticancer activity of carboxylated gallium corroles

“…Of interest here is a gallium(III) complex, 1 [Ga(tpfc)] (32)(33)(34)(35), where tpfc represents the trianion of 5,10,15-tris(pentafluorophenyl)corrole [H 3 (tpfc)]. 1 is highly fluorescent, with an emission quantum yield far exceeding that of its zinc porphyrin analog (36)(37)(38). The macrocyclic ring of this complex can be selectively modified to afford molecules that exhibit a wide range of physical and chemical properties (1).…”

Cellular uptake and cytotoxicity of a near-IR fluorescent corrole–TiO2 nanoconjugate

“…The PMH were more susceptible to the cytotoxic effects of 1-Al -TiO 2 than the U87-Luc cells; it is reasonable that non-cancerous cells, especially primary cells, would be less tolerant towards exogenous non-native agents[48,49]. Nonetheless, the intense fluorescence exhibited by 1-Al [26,33] would allow for the potential use of the nanoconjugate 1-Al -TiO 2 as an optical imaging agent observable by confocal fluorescence microscopy even at low concentrations (0.02–2 µg/mL) below the cytotoxic thresholds for both cancerous and non-cancerous cells.…”

“…Many studies have shown that 5,10,15-trispentafluorophenyl corrole and its derivatives exhibit bright and robust fluorescence signals in the near-IR region (λ em ≥ 600 nm) and are therefore considered suitable candidates for optical imaging[20–23]. In addition, the chemical versatility of corroles, allowing for various metallation[24–26] and substitution[27,28] reactions, as well as their biological stability[29–31] make them attractive contrast agents.…”

“…Because 1-Al -TiO 2 exhibits the brightest fluorescence, consistent with the emission properties of related molecular Al corroles[26,32,33], we chose this nanoconjugate as a model to study cellular uptake and cytotoxic effects.…”