Comprehensive review of photophysical parameters (ε, Φf, τs) of tetraphenylporphyrin (H2TPP) and zinc tetraphenylporphyrin (ZnTPP) – Critical benchmark molecules in photochemistry and photosynthesis

Taniguchi, Masahiko; Lindsey, Jonathan S.; Bocian, David F.; Holten, Dewey

doi:10.1016/j.jphotochemrev.2020.100401

Cited by 122 publications

(95 citation statements)

References 872 publications

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“… a Fluorescence quantum yield was calculated relative to meso -tetraphenylporphyrin (TPP) in CH 2 Cl 2 (ϕ f of TPP was taken as 0.13 in CH 2 Cl 2 ). 33 b ϕ ISC was calculated from ns–ms transient absorption kinetics. ϕ ISC was calculated by comparing the ground-state bleach amplitude immediately after the excitation and its remaining amplitude in the 100 ns range.…”

Section: Resultsmentioning

confidence: 99%

Tailoring the Intersystem Crossing and Triplet Dynamics of Free-Base Octaalkyl-β-oxo-Substituted Porphyrins: Competing Effects of Spin–Vibronic and NH Tautomerism Relaxation Channels

et al. 2022

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We demonstrate that β-oxo-substitution provides effective fine-tuning of both steady-state and transient electronic properties of octaalkyl-β-mono-oxochlorin and all isomers of the β,β′-dioxo-substituted chromophores. The addition of a carbonyl group increases the Q y oscillator strength and red-shifts the absorption spectra. Each oxo-substitution results in a 2-fold increase in the singlet to triplet state intersystem crossing (ISC) rates, resulting in a 4-fold ISC rate increase for the dioxo-substituted chromophores. The effects of oxo-substitution on the ISC rate are thus additive. The progressive increase in the ISC rates correlates directly with the spin–vibronic channels provided by the C=O out-of-plane distortion modes, as evidenced by density functional theory (DFT) modeling. The triplet states, however, were not evenly affected by β-oxo-substitution, and reduction in the triplet lifetime seems to be influenced instead by the presence of NH tautomers in the dioxoisobacteriochlorins.

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Section: Resultsmentioning

confidence: 99%

Tailoring the Intersystem Crossing and Triplet Dynamics of Free-Base Octaalkyl-β-oxo-Substituted Porphyrins: Competing Effects of Spin–Vibronic and NH Tautomerism Relaxation Channels

et al. 2022

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“…19,20,25,53 Our result rather corresponds to the lifetimes in less polar solutions agreeing with the negligible influence of the solvent on the Q x lifetime, which has recently been established in a review of TPP (and ZnTPP) photophysical properties. 54 Instead, the O 2 saturation of the solution has been considered as the dominant factor – leading to a 23% decrease – of the lifetime of the lowest singlet excited state. However, one of the shorter TCPP lifetimes 19 has been determined in de-aerated solutions, while one of the longer ones in air-equilibrated solution.…”

Section: Resultsmentioning

confidence: 99%

Fundamental electronic changes upon intersystem crossing in large aromatic photosensitizers: free base 5,10,15,20-tetrakis(4-carboxylatophenyl)porphyrin

Büchner

Cruz

Grover

et al. 2022

Phys. Chem. Chem. Phys.

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“…Since this experimental work was done, we re‐examined the literature data for dioxobacteriochlorin‐type tolyporphins (e.g., tolyporphin A) and concluded that a value of 100 000 M ‐1 cm ‐1 was more reasonable. We also examined the ɛ values for diverse chlorophylls (22) and the related benchmark macrocycles meso ‐tetraphenylporphyrin and meso ‐tetraphenylporphinatozinc(II) (33). The reported ɛ values for tetrapyrroles vary over a large range and often are underestimated; indeed, values of ɛ significantly larger than that employed here for chlorophyll a also are known (e.g., 89 800 M ‐1 cm ‐1 (34)).…”

Section: Discussionmentioning

confidence: 99%

Fluorescence Assay for Tolyporphins Amidst Abundant Chlorophyll in Crude Cyanobacterial Extracts

Nguyen

Zhang

Taniguchi

et al. 2021

Photochem & Photobiology

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Tolyporphins are distinctive tetrapyrrole natural products found singularly in a filamentous cyanobacterial‐microbial holobiont (termed HT‐58‐2) from Micronesia. The absorption and fluorescence features of tolyporphins resemble those of chlorophyll a, complicating direct analysis of culture samples. Treatment of the crude (unfractionated) organic extract (CH2Cl2/2‐propanol, 1:1) of HT‐58‐2 cultures with NaBH4 in methanol causes reduction of the peripheral ketone auxochromes, whereupon tolyporphins (predominantly 7,17‐dioxobacteriochlorins) exhibit a bathochromic shift (λabs ˜ 676 → ˜ 700 nm) and chlorophyll a (a 131‐oxochlorin) exhibits a hypsochromic shift (λabs 665 → 634 nm). Fluorescence excitation spectroscopy (at 368 and 491 nm with λem 710 nm) enabled detection of reduced tolyporphins amidst abundant reduced chlorophyll a (1:19 ratio), a detection sensitivity >5 times that without reduction. The resulting assay combines simple sample preparation from non‐axenic cultures at microscale quantities (2 mL, 2 μm), absence of any fractionation procedures, and fluorescence detection. Tolyporphins were readily detected in cultures of HT‐58‐2 at reasonable growth periods in the absence of environmental stressors, which was not possible previously.

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Comprehensive review of photophysical parameters (ε, Φf, τs) of tetraphenylporphyrin (H2TPP) and zinc tetraphenylporphyrin (ZnTPP) – Critical benchmark molecules in photochemistry and photosynthesis

Cited by 122 publications

References 872 publications

Tailoring the Intersystem Crossing and Triplet Dynamics of Free-Base Octaalkyl-β-oxo-Substituted Porphyrins: Competing Effects of Spin–Vibronic and NH Tautomerism Relaxation Channels

Tailoring the Intersystem Crossing and Triplet Dynamics of Free-Base Octaalkyl-β-oxo-Substituted Porphyrins: Competing Effects of Spin–Vibronic and NH Tautomerism Relaxation Channels

Fundamental electronic changes upon intersystem crossing in large aromatic photosensitizers: free base 5,10,15,20-tetrakis(4-carboxylatophenyl)porphyrin

Fluorescence Assay for Tolyporphins Amidst Abundant Chlorophyll in Crude Cyanobacterial Extracts

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