Tuning Chemical and Physical Properties of Phosphorus Corroles for Advanced Applications

Abstract

Although the affinity of metallocorroles to axial ligands is quite low,t his is not the case when the chelated element is phosphorus. This work is hence focusedo nt he mechanism of ligand exchange of six-coordinate phosphorus corroles as at ool for affecting their chemical and physical properties. These fundamental investigations allowed for the development of facile methodologies for the synthesis of a large series of complexes and the establishment of several new structure/activity profiles that may be used to understand and predict spectroscopic features and for tailor-made modification of photophysical and electrochemical properties. This is exemplified by the facile access to complexes with terminal groups that are of large potentialf or practical applicationsb ased on click chemistry,o ptical imaging, and surfacescience.Scheme1.Oxo-, hydroxo-and trans-bishydroxo-P V chelated by corrole, porphyrin, or phthalocyanine.[a] Q.

Corroles and Hexaphyrins: Synthesis and Application in Cancer Photodynamic Therapy

“…Axial ligand exchange is another way to modulate the properties of phosphorus corrole complexes. The treatment of corrole dihydroxophosphorus (V) complex 54 with the appropriate alcohol in presence of TFA, at room temperature during 10 min, afforded corrole complexes 55 in high yields (80–95%) ( Scheme 21 ) [ 58 ]. This acid-catalyzed ligand exchange was followed by uv-vis and 31 P-NMR spectroscopy analyses.…”

MCD and MCPL Characterization of Luminescent Si(IV) and P(V) Tritolylcorroles: The Role of Coordination Number

“…A similar titration has been conducted also by propanol addition (Figure S1), where the complex conversion seems to be a little more difficult (i.e., it requires a larger amount of alcohol to shift the equilibrium) compared to that observed with methanol or by performing TFA-promoted axial ligand exchange …”

“…A similar titration has been conducted also by propanol addition (Figure S1), where the complex conversion seems to be a little more difficult (i.e., it requires a larger amount of alcohol to shift the equilibrium) compared to that observed with methanol or by performing TFA-promoted axial ligand exchange. 46 The same process can be also followed by fluorescence (Figure 2C). In CH 2 Cl 2 solution, (TTC)P(OH) 2 displays a fluorescence spectrum composed of two bands, one at 576 nm (2.15 eV) and one at 614 nm (2.02 eV).…”

Corrole-Substituted Fluorescent Heme Proteins

“…If this were the case, it would be expected that this is a general phenomenon for all P­(V) corroles. However, six-coordinate P corroles and related analogues exhibit longer singlet excited state lifetimes (3–4 ns). − Alternatively, the weak fluorescence of P-2 likely reflects differences in phosphorus speciation. Five-coordinate meso -triaryl corroles can be obtained by treating the six-coordinate complex with TFA, and it was shown that this five-coordinate species exhibits a lower fluorescence quantum yield (27%) and shorter excited-state lifetime (1.61 ns) than the analogous six-coordinate complex (ϕ = 44%, τ = 3.01 ns) .…”