Gold Tris(carboxyphenyl)corroles as Multifunctional Materials: Room Temperature Near-IR Phosphorescence and Applications to Photodynamic Therapy and Dye-Sensitized Solar Cells

Abstract

Two amphiphilic corroles-5,10,15-tris(3-carboxyphenyl)corrole (H3[mTCPC]) and 5,10,15-tris(4-carboxyphenyl)corrole (H3[pTCPC])-and their gold complexes have been synthesized, and their photophysical properties and photovoltaic behavior have been investigated. Like other nonpolar gold corroles, Au[mTCPC] and Au[pTCPC] were both found to exhibit room temperature phosphorescence in deoxygenated solutions with quantum yields of ∼0.3% and triplet lifetimes of ∼75 μs. Both compounds exhibited significant activity as dyes in photodynamic therapy experiments and in dye-sensitized solar cells. Upon irradiation at 435 nm, both Au corroles exhibited significant phototoxicity against AY27 rat bladder cancer cells while the free-base corroles proved inactive. Dye-sensitized solar cells constructed using the free bases H3[mTCPC] and H3[pTCPC] exhibited low efficiencies (≪1%), well under that obtained with 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin, H2[pTCPP] (1.9%, cf. N719 9.5%). Likewise, Au[pTCPC] proved inefficient, with an efficiency of ∼0.2%. By contrast, Au[mTCPC] proved remarkably effective, exhibiting an open-circuit voltage (Voc) of 0.56 V, a short-circuit current of 8.7 mA cm(-2), a fill factor of 0.72, and an efficiency of 3.5%.

Gold dipyrrin-bisphenolates: a combined experimental and DFT study of metal–ligand interactions

“…4). 25,26 Cyclic voltammetric measurements, indicating relatively high oxidation potentials of around +0.95 V against the saturated calomel electrode (SCE), 27 relatively low reduction potentials of around À0.90 V, and substantial electrochemical HOMO-LUMO gaps of around 1.85 V, are also suggestive of an innocent description for the Au[XDPP] complexes ( Fig. 5).…”

Corrole‐based photodynamic antitumor therapy

“…In the past two decades, corrole chemistry has received much attention as indicated by a steady increase of the SCI publications on corrole (Figure ). Corrole derivatives have demonstrated extensive usage in catalytic oxidation, synthetic organic reaction, electrocatalytic hydrogen evolution, chemical sensors, dye sensitized solar cells, and antitumor drugs …”

Grafting Copper and Gallium Corroles onto Zinc Oxide Nanoparticles

“…Over the last few years corroles have proved to be outstanding light-harvesting materials, on surfaces or for solar cells. [1][2][3] These pyrrole-based macrocycles have demonstrated impressive synthetic versatility, allowing a fine tunability of their photophysical properties. [4][5][6][7][8][9] In order to improve the harvesting of solar energy in a broad spectral region, it is important to extend the corrole energy absorption across the visible spectrum as much as possible.…”