Phosphorus corrole complexes: from property tuning to applications in photocatalysis and triplet–triplet annihilation upconversion

Mahammed, Atif; Chen, Kepeng; Vestfrid, Jenya; Zhao, Jianzhang; Gross, Zeev

doi:10.1039/c9sc01463b

Cited by 52 publications

(52 citation statements)

References 85 publications

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“…Gross and Zhao also described the synthesis and photophysical properties of fluorinated phosphorus corrole complexes 32 and the corresponding β-iodo-substituted derivatives 34 [ 46 ] . The preparation of complexes 32 was achieved in quantitative yield by the axial hydroxyl ligand exchange of complexes 31 with fluorides, upon reaction with aqueous hydrofluoric acid ( Scheme 12 ).…”

Section: Functionalization At the Inner Core And Peripheral Positimentioning

confidence: 99%

Corroles and Hexaphyrins: Synthesis and Application in Cancer Photodynamic Therapy

2020

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Corroles and hexaphyrins are porphyrinoids with great potential for diverse applications. Like porphyrins, many of their applications are based on their unique capability to interact with light, i.e., based on their photophysical properties. Corroles have intense absorptions in the low-energy region of the uv-vis, while hexaphyrins have the capability to absorb light in the near-infrared (NIR) region, presenting photophysical features which are complementary to those of porphyrins. Despite the increasing interest in corroles and hexaphyrins in recent years, the full potential of both classes of compounds, regarding biological applications, has been hampered by their challenging synthesis. Herein, recent developments in the synthesis of corroles and hexaphyrins are reviewed, highlighting their potential application in photodynamic therapy.

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Section: Functionalization At the Inner Core And Peripheral Positimentioning

confidence: 99%

Corroles and Hexaphyrins: Synthesis and Application in Cancer Photodynamic Therapy

2020

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“…Absorption spectra have been obtained as vertical electronic excitations from the structural minima of the ground state by substituting the 6‐31G* basis set with the 6‐31+G* one. Solvent effects have been included by using the nonequilibrium implementation of the polarizable continuum model in its linear response (LR) formalism in toluene ( ε = 2.37), the same solvent used in the reference experimental study . Performances of two XC functionals used have been evaluated comparing absorption electronic spectra with available experimental data …”

Section: Computational Detailsmentioning

confidence: 99%

“…Due to their relatively easy synthetic accessibility and some peculiar properties, phosphorus (V) corrole complexes have been proposed for a series of interesting applications in the fields of catalysis, chemical sensors, triplet photosensitizers, molecular spintronics, and PDT . Recently, the triplet quantum yield of a series of Iodine substituted phosphorus corrole complexes has been experimentally detected . Herein we present a detailed theoretical study that allows to suggest their use in PDT.…”

Section: Introductionmentioning

confidence: 99%

Iodine substituted phosphorus corrole complexes as possible photosensitizers in photodynamic therapy: Insights from theory

et al. 2020

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The search for new dyes to be used as photosensitizers in photodynamic therapy (PDT) is a field of great interest from both experimental and theoretical viewpoints.In this study, the main photophysical properties (excitation energies, singlet-triplet energy gap, and spin orbit coupling matrix elements) of some unsubstituted and iodine substituted phosphorus corrole complexes have been determined by using density functional theory and its time-dependent formulation. Results show that these compounds can be proposed as photosensitizers in PDT. The heavy atom effects have been rationalized on the basis of El-Sayed rules. K E Y W O R D S DFT, heavy atom effect, PDT, phosphorus corrole complexes, TDDFT 1PF2-I4 555 [0.230] 548 [0.238] 589 [0.62] 545 [0.134] 535 [0.114] 544 [0.15] 403 [1.120] 403 [1.048] 423 [2.80] 2PF2-I3 552 [0.274] 540 [0.252] 587 [0.61] 531 [0.072] 521 [0.063] 570 [0.42] 400 [1.446] 399 [1.398] 415 [2.88] 2PF2-I4 558 [0.269] 553 [0.275] 587 [0.61] 541 [0.123] 533 [0.103] 570 [0.42] 402 [1.427] 406 [0.498] 417 [3.06] Note: Experimental values are taken from Ref. [12].

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“…The triplet state can phosphorescence, or initiate energy or electron transfer. Triplet PSs have been widely used in photocatalysis, [4][5][6] photodynamic therapy, [7][8][9][10] photovoltaics, [11] and photon upconversion [12][13][14][15][16][17][18].…”

Section: Introductionmentioning

confidence: 99%

Charge separation, charge recombination and intersystem crossing in orthogonal naphthalimide–perylene electron donor/acceptor dyad

Chen

Pang

Imran

et al. 2021

Photochem Photobiol Sci

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We prepared an orthogonal electron donor/acceptor dyad (NI-Py) with perylene (Py) as electron donor and 4-aminonaphthalimide (NI) as an electron acceptor. The molecule adopts orthogonal geometry due to the steric hindrance exerted by the 4-amino substituents on the NI moiety. The photophysical properties of dyad were studied by steady-state UV-Vis absorption and fluorescence spectroscopies, femtosecond/nanosecond transient absorption spectroscopies and DFT computations. Ground state interaction between the NI and Py units is negligible; however, charge separation occurs upon photoexcitation, indicated by the quenching of the fluorescence of the dyad in polar solvents, i.e. fluorescence quantum yield (Φ F ) is 61.9% in toluene and Φ F = 0.2% in methanol. Spin-orbit-coupled charge transfer-induced intersystem crossing (SOCT-ISC) was confirmed by femtosecond transient absorption spectroscopy (charge separation takes 1.7 ps and charge recombination takes 6.9 ns, in CH 2 Cl 2 ). Nanosecond transient absorption spectra indicated the formation of perylene-localized triplet state, and the triplet state lifetime (175 μs) is much longer than that accessed with the heavy atom effect (3-bromoperylene; 16 μs). The singlet oxygen quantum (Φ Δ ) yield of the dyad is 2.2% in hexane and 9.5% in dichloromethane. The low SOCT-ISC efficiency as compared to the previously reported analogue (Φ Δ = 80%) is attributed to the mismatch of the 1 CT/T n state energies, and/or the orientation of the NI and Py units, i.e. orthogonal geometry is not sufficient for achieving efficient SOCT-ISC in compact electron donor/acceptor dyads.

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Phosphorus corrole complexes: from property tuning to applications in photocatalysis and triplet–triplet annihilation upconversion

Abstract: Hypothesis driven design leads to metal-free corroles that display excellent performance for photo-induced reduction, oxidation and energy transfer, and also serve as superb catalysts for photoredox organic reactions and triplet–triplet annihilation upconversions.

Cited by 52 publications

References 85 publications

Corroles and Hexaphyrins: Synthesis and Application in Cancer Photodynamic Therapy

Corroles and Hexaphyrins: Synthesis and Application in Cancer Photodynamic Therapy

Iodine substituted phosphorus corrole complexes as possible photosensitizers in photodynamic therapy: Insights from theory

Charge separation, charge recombination and intersystem crossing in orthogonal naphthalimide–perylene electron donor/acceptor dyad

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