Photophysical Properties and Electronic Structure of Chlorin-Imides: Bridging the Gap between Chlorins and Bacteriochlorins

Faries, Kaitlyn M.; Diers, James R.; Springer, Joseph W.; Yang, Eunkyung; Ptaszek, Marcin; Lahaye, Dorothée; Krayer, Michael; Taniguchi, Masahiko; Kirmaier, Christine; Lindsey, Jonathan S.; Bocian, David F.; Holten, Dewey

doi:10.1021/jp511257w

Cited by 24 publications

(32 citation statements)

References 87 publications

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“…The chlorin-imides thus fill the gap in the spectral progression of synthetic free base and zinc chlorins lacking imides (598–687 nm; Figures 5 and 6), chlorin-imides (660–714 nm) 300 and synthetic bacteriochlorins (709 to nearly 900 nm). 348,390 …”

Section: Bromination Of Chlorinsmentioning

confidence: 84%

“…Efforts to fulfill such objectives over the past 20 years have been described in 45 papers (including >1200 pages of Supporting Information). 254–300 …”

Section: Development Of De Novo Syntheses Of Gem-dialkylchlorinsmentioning

confidence: 99%

“…265 Such a display relies on the peak amplitude of the B band (I B ) against which the variation of peak amplitude of the Q y band (I Qy ) can be assessed. Alternative measures rely on the ratio of the integrated absorption band manifolds (Σ Qy /Σ B , when plotted vs cm −1 ) 300 or even the fraction of absorption by the Q y band relative to that of the entire absorption spectrum (ΣQ y /ΣT). 348 …”

Section: Importance and Synthetic Challenges Of β-Pyrrole Substitumentioning

confidence: 99%

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De NovoSynthesis of Gem-Dialkyl Chlorophyll Analogues for Probing and Emulating Our Green World

2015

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Woodward reported his infamous synthesis of chlorin e 6 trimethyl ester, a known synthetic precursor to chlorophyll a. [59][60][61][62][63][64]124 The work was posited on a half-century of intensive studies by many investigators in tetrapyrrole chemistry and began a decade after the close of Fischer's lifetime of research 125−128 (which included an uncompleted synthetic program directed toward chlorophylls 15 ). Indeed, "he read all the umpteen papers on the chlorophylls written by Willstaẗter and Fischer, including the experimental parts." 129 The Woodward synthesis of chlorin e 6 trimethyl ester required 46 steps, of which 24 were spent on converting the sole precursor, Knorr's pyrrole, to the four pyrroles destined to form rings A−D; 7 additional steps accrued to obtain the dipyrromethanes that constitute the Eastern and Western halves (Scheme 13, the step numbers are identical to those shown in ref 64.). The first step formed the Knorr pyrrole (in several kg quantities), the next 24 steps were divided into four parallel paths, whereas the remaining 21 steps proceeded in linear fashion. Remarkable features of the synthesis include the directed intramolecular joining (via an imine) of the Eastern and Western halves (step 33), construction of the acrylate Scheme 10. Hydrogenation of a Porphyrin to Form a Chlorin Scheme 11. Representative meso-Tetraarylchlorins Scheme 12. Methyl Pyropheophorbide a

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Section: Bromination Of Chlorinsmentioning

confidence: 84%

“…Efforts to fulfill such objectives over the past 20 years have been described in 45 papers (including >1200 pages of Supporting Information). 254–300 …”

Section: Development Of De Novo Syntheses Of Gem-dialkylchlorinsmentioning

confidence: 99%

Section: Importance and Synthetic Challenges Of β-Pyrrole Substitumentioning

confidence: 99%

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De NovoSynthesis of Gem-Dialkyl Chlorophyll Analogues for Probing and Emulating Our Green World

2015

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“…For example, our prior studies have examined the effect of substituents at the 2,3,12,13‐positions on the four frontier MOs (HOMO‐1, HOMO, LUMO, LUMO+1), which are thought to dominate the spectral properties of tetrapyrroles as described by the four‐orbital model . The results generally show a preferential effect on the LUMO energy and thus the LUMO−HOMO gap, which for bacteriochlorins makes the major contribution to the energy/wavelength of the S 1 ( Q y )‐excited state . [Effects on the LUMO+1−HOMO‐1 along with LUMO−HOMO contribute to the Q y intensity.]…”

Section: Discussionmentioning

confidence: 99%

Integration of Cyanine, Merocyanine and Styryl Dye Motifs with Synthetic Bacteriochlorins

Yang

Zhang

Krayer

et al. 2015

Photochem & Photobiology

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Understanding the effects of substituents on spectral properties is essential for the rational design of tailored bacteriochlorins for light-harvesting and other applications. Toward this goal, three new bacteriochlorins containing previously unexplored conjugating substituents have been prepared and characterized. The conjugating substituents include two positively charged species, 2-(N-ethyl 2-quinolinium)vinyl- (B-1) and 2-(N-ethyl 4-pyridinium)vinyl- (B-2), and a neutral group, acroleinyl- (B-3); the charged species resemble cyanine (or styryl) dye motifs whereas the neutral unit resembles a merocyanine dye motif. The three bacteriochlorins are examined by static and time-resolved absorption and emission spectroscopy and density functional theoretical calculations. B-1 and B-2 have Qy absorption bathochromically shifted well into the NIR region (822 and 852 nm), farther than B-3 (793 nm) and other 3,13-disubstituted bacteriochlorins studied previously. B-1 and B-2 have broad Qy absorption and fluorescence features with large peak separation (Stokes shift), low fluorescence yields, and shortened S1 (Qy ) excited-state lifetimes (~700 ps and ~100 ps). More typical spectra and S1 lifetime (~2.3 ns) are found for B-3. The combined photophysical and molecular-orbital characteristics suggest the altered spectra and enhanced nonradiative S1 decay of B-1 and B-2 derive from excited-state configurations in which electron density is shifted between the macrocycle and the substituents.

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“…The decreased tetrapyrrole symmetry is responsible for the intense chlorin absorption in the red, which porphyrins lack (Figure 1b). [5][6][7] For example, the recently discovered chlorophyll f differs from chlorophyll a only in having a 2-CHO substituent instead of a 2-Me ( Figure 1a). [5][6][7] For example, the recently discovered chlorophyll f differs from chlorophyll a only in having a 2-CHO substituent instead of a 2-Me ( Figure 1a).…”

Section: Introductionmentioning

confidence: 99%

Isolation and Characterization of a Monoprotonated Hydroporphyrin

et al. 2018

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A simple protocol for the controlled preparation of mono‐ and diprotonated hydroporphyrins (chlorins) is presented. The chlorins carried 10‐aryl groups with electron‐neutral (phenyl), electron‐donating (p‐OMe‐C6H4) or electron‐withdrawing (pentafluorophenyl) substituents. The protonation reactions were readily followed by UV/Vis absorption spectroscopy, enabling the determination of the first (4.8–5.3) and second pKa's (1.7–0.5). Both mono‐ and diprotonated species were fully characterized by 1H NMR spectroscopy, which, in combination with theoretical studies, showed that these macrocycles were significantly distorted in solution. A 10‐phenyl‐substituted monoprotonated chlorin was characterized by X‐ray crystallography. This is the first structurally characterized hydroporphyrin monocation, and the first crystal structure of a sterically unencumbered singly protonated tetrapyrrole. The photostabilities of the mono‐ and diprotonated 10‐phenylchlorins were measured upon irradiation into their Soret bands; protonation yielded increased photostabilities.

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Photophysical Properties and Electronic Structure of Chlorin-Imides: Bridging the Gap between Chlorins and Bacteriochlorins

Cited by 24 publications

References 87 publications

De NovoSynthesis of Gem-Dialkyl Chlorophyll Analogues for Probing and Emulating Our Green World

De NovoSynthesis of Gem-Dialkyl Chlorophyll Analogues for Probing and Emulating Our Green World

Integration of Cyanine, Merocyanine and Styryl Dye Motifs with Synthetic Bacteriochlorins

Isolation and Characterization of a Monoprotonated Hydroporphyrin

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