The effect of central metal on the photodynamic properties of silylated tetraphenylporphyrin derivative

Horiuchi, Hiroaki; Terashima, Keisuke; Sakai, Asumi; Suda, Daisuke; Yoshihara, Toshitada; Kobayashi, Atsushi; Tobita, Seiji; Okutsu, Tetsuo

doi:10.1016/j.jphotochem.2016.01.004

Cited by 15 publications

(8 citation statements)

References 30 publications

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“…This reveals a significant perturbation of the emission properties of the free-base component in the monometallated cages due to the presence of the Zn-porphyrin counterpart. A possible explanation is the close proximity of the Zn center of the metallated porphyrin to the core of the free-base partner, which can lead to a change in molecular symmetry or to an increased intersystem crossing rate [35][36][37] in the latter.…”

Section: Photophysical Characterizationmentioning

confidence: 99%

Photophysical properties of porphyrinic covalent cages endowed with different flexible linkers

Sánchez-Resa

Schoepff

Djemili

et al. 2019

J. Porphyrins Phthalocyanines

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In-depth photophysical studies of four flexible covalent cages bearing either two free-base porphyrins or one free-base porphyrin and one Zn(II) porphyrin, connected by linkers of different lengths, are reported. In the case of the cages with two free-base porphyrins, exciton coupling between the porphyrins is evidenced by large and split Soret bands in the absorption spectra, but the different length of the linkers has only a slight effect on their emission properties. Strong electronic interactions between the porphyrins are also evidenced for the cages that incorporate a free-base porphyrin and a Zn(II) porphyrin, with a more pronounced splitting of the Soret band for the system with longer linkers. In these cages, following excitation of the Zn-porphyrin component, an almost quantitative energy transfer to the free-base unit occurs, with a rate 1.4 times faster in the cage with longer linkers (1.4 × 10[Formula: see text] s[Formula: see text] vs. 1.0 × 10[Formula: see text] s[Formula: see text]. This difference might reflect the more flattened conformation adopted by the cage equipped with longer and more flexible linkers, the latter allowing for a shorter interplanar distance between the porphyrins. The results are discussed in terms of classical and short-range energy transfer mechanisms.

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Section: Photophysical Characterizationmentioning

confidence: 99%

Photophysical properties of porphyrinic covalent cages endowed with different flexible linkers

Sánchez-Resa

Schoepff

Djemili

et al. 2019

J. Porphyrins Phthalocyanines

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show abstract

“…This value is close to the reported values for PdTPP (0.96 ± 0.04) 42 and PdTPP derivative with sodium carbonate and trimethylsilyl (0.90 ± 0.10). 43 Since the nonradiative rate constant k nr of metallo-TPP is in the order of 10 8 s −1 (e.g., 5.1 × 10 8 s −1 for ZnTPP 46 ), the fluorescence rate constant k f of PdTPP is in the order of 10 7 − 10 8 s −1 (e.g., 1.7 × 10 7 s −1 for PdTPP 47 and 1.5 × 10 8 s −1 for Pd-tetraphenylantroporphyrin 25 ), and the inverse of the singlet lifetime τ S −1 = k f + k nr + k ISC is around 10 11 s −1 (from τ s = 20 ps for PdTPP 47 and 2.9 ps for Pd-tetraphenylantroporphyrin 25 ), ISC can be considered as the dominant deactivation path for PdTPP compounds. This is not conflicting with Φ ISC close to unity.…”

Section: Energy Matching Condition For Tetmentioning

confidence: 99%

Solution to the Host–Guest Compatibility Problem of Solid Triplet–Triplet Annihilation Photon Upconversion by a Molecular-Anchor Sensitizer Approach

Fukuuchi,

Toyoshima,

Yoshinami

et al. 2024

J. Phys. Chem. C

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Efficient and uniform solid-state triplet−triplet annihilation photon upconversion (TTA-UC) is demonstrated by the solution cast film doped with the emitter-tethered sensitizer, in which the emitter part acts as a molecular anchor to control segregation of guest sensitizer molecules from the host matrix of emitter molecules on solidification. The tethered sensitizer, named as molecular-anchor sensitizer (MAS), was implemented as the supramolecules consisting of Pd-tetraphenylporphyrin (PdTPP) unit as the core and 4 or 8 units of 9,10-diphenylanthracene (DPA) tethered to the core with a flexible molecular chain. Saturated solution of DPA doped with a tiny amount of MAS (1:1000 or less in a molar ratio) was used for casting. The solid films fabricated from this solution showed good uniformity of upconversion (UC) emission. Most crystalline grains showed intense UC emission by 532 nm excitation, while a small number of crystalline grains showed UC emission for the film with a conventional (nontethered) sensitizer. The UC quantum yield (UC-QY, 50% basis) of the solid film with MAS was found to be 0.01−0.02 at a molar ratio of sensitizer to emitter of 1:1000. It was found that a decrease of the sensitizer concentration suppressed the fluorescence quenching of DPA by the sensitizer and the UC-QY increased to 0.13. The internal quantum yield, which is the quotient of doubled UC-QY divided by the fluorescence quantum yield, was found to depend on the number and length of the tether of MAS and to be close to unity for the sensitizers with fewer (4) and longer (C 6 ) tethers regardless of the kind. The concept of MAS opens a new way for further development of efficient solid TTA-UC systems by providing better compatibility between the sensitizer and the emitter in the solid matrix.

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Section: Photophysical Characterizationmentioning

confidence: 99%

Photophysical properties of porphyrinic covalent cages endowed with different flexible linkers

Sánchez-Resa

Schoepff

Djemili

et al. 2021

Porphyrin Science by Women

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In-depth photophysical studies of four flexible covalent cages bearing either two freebase porphyrins or one free-base porphyrin and one Zn(II) porphyrin, connected by linkers of different lengths, are reported. In the case of the cages with two free-base porphyrins, exciton coupling between the porphyrins is evidenced by large and split Soret bands in the absorption spectra, but the different length of the linkers has only a slight effect on their emission properties. Strong electronic interactions between the porphyrins are also evidenced for the cages that incorporate a free-base porphyrin and a Zn(II) porphyrin, with a more pronounced splitting of the Soret band for the system with longer linkers. In these cages, following excitation of the Zn-porphyrin component, an almost quantitative energy transfer to the free-base unit occurs, with a rate 1.4 times faster in the cage with longer linkers (1.4 × 10 11 s -1 vs. 1.0 × 10 11 s -1 ). This difference might reflect the more flattened conformation adopted by the cage equipped with longer and more flexible linkers, the latter allowing for a shorter interplanar distance between the porphyrins. The results are discussed in terms of classical and short-range energy transfer mechanisms.

show abstract

The effect of central metal on the photodynamic properties of silylated tetraphenylporphyrin derivative

Cited by 15 publications

References 30 publications

Photophysical properties of porphyrinic covalent cages endowed with different flexible linkers

Photophysical properties of porphyrinic covalent cages endowed with different flexible linkers

Solution to the Host–Guest Compatibility Problem of Solid Triplet–Triplet Annihilation Photon Upconversion by a Molecular-Anchor Sensitizer Approach

Photophysical properties of porphyrinic covalent cages endowed with different flexible linkers

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