De novo synthesis and photophysical characterization of annulated bacteriochlorins. Mimicking and extending the properties of bacteriochlorophylls

Krayer, Michael; Yang, Eunkyung; Diers, James R.; Bocian, David F.; Holten, Dewey; Lindsey, Jonathan S.

doi:10.1039/c0nj00771d

Cited by 40 publications

(84 citation statements)

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“…As described above, the same is true of the bacteriochlorins bearing 3,13 substituents that are the focus of this work and our recent investigation of the PDT efficacy of these photosensitizers . On the basis of shifts in MO energy and redox properties obtained upon incorporation of cyano versus acetyl groups at similar positions (Table ) , one would expect the combined effects on oxidation potentials [photostability and photoactivity via Eq. (1A)] and reduction potentials [photoactivity via Eq.…”

Section: Resultsmentioning

confidence: 74%

“…Such trends can be seen in the redox properties and the energies of the frontier molecular orbitals (Table ) . Furthermore, the strategic choice and placement of substituents allow some control over the relative oxidation and reduction potentials ( via HOMO and LUMO energies), as has been shown for synthetic chlorins, bacteriochlorins and related oxophorbines and bacteriooxophorbines that incorporate the keto‐bearing five‐membered ring of the native photosynthetic chromophores .…”

Section: Resultsmentioning

confidence: 95%

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Molecular Electronic Tuning of Photosensitizers to Enhance Photodynamic Therapy: Synthetic Dicyanobacteriochlorins as a Case Study

Yang

Diers

Huang

et al. 2013

Photochem & Photobiology

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Photophysical, photostability, electrochemical, and molecular-orbital characteristics are analyzed for a set of stable dicyanobacteriochlorins that are promising photosensitizers for photodynamic therapy (PDT). The bacteriochlorins are the parent compound (BC), dicyano derivative (NC)2BC and corresponding zinc (NC)2BC-Zn and palladium chelate (NC)2BC-Pd. The order of PDT activity against HeLa human cancer cells in vitro is (NC)2BC-Pd > (NC)2BC > (NC)2BC-Zn ≈ BC. The near-infrared absorption feature of each dicyanobacteriochlorin is bathochromically shifted 35–50 nm (748–763 nm) from that for BC (713 nm). Intersystem crossing to the PDT-active triplet excited state is essentially quantitative for (NC)2BC-Pd. Phosphorescence from (NC)2BC-Pd occurs at 1122 nm (1.1 eV). This value and the measured ground-state redox potentials fix the triplet excited-state redox properties, which underpin PDT activity via Type-1 (electron-transfer) pathways. A perhaps counterintuitive (but readily explicable) result is that of the three dicyanobacteriochlorins, the photosensitizer with the shortest triplet lifetime (7 μs), (NC)2BC-Pd, has the highest activity. Photostabilities of the dicyanobacteriochlorins and other bacteriochlorins studied recently are investigated and discussed in terms of four phenomena: aggregation, reduction, oxidation, and chemical reaction. Collectively, the results and analysis provide fundamental insights concerning the molecular design of PDT agents.

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Section: Resultsmentioning

confidence: 74%

Section: Resultsmentioning

confidence: 95%

Molecular Electronic Tuning of Photosensitizers to Enhance Photodynamic Therapy: Synthetic Dicyanobacteriochlorins as a Case Study

Yang

Diers

Huang

et al. 2013

Photochem & Photobiology

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“…Lindsey's group introduced a range of fully synthetic chlorin‐ and bacteriochlorin‐type chromophores that incorporate an N ‐substituted ring E imide, such as chlorin 13 33,34. The authors cited the bathochromic shifts, the stabilization the annulated imide imparts toward routine handling, and the ability to introduce diverse groups at the nitrogen atom of the imide as the main driving forces for the development of synthetic methods for the establishment of the imide into synthetic hydroporphyrins.…”

Section: Resultsmentioning

confidence: 99%

Expansion of a Pyrrole in meso‐Tetraphenylporphyrin to a Pyrazine Imide Moiety Using a Beckmann Rearrangement

Akhigbe

Brückner

2013

Eur J Org Chem

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The group 10 metal complexes of β,β′‐dioxoporphyrin monooxime 10M (M = NiII, PdII, PtII) are susceptible to a Beckmann rearrangement to produce the corresponding ring‐expanded metallopyrazinoporphyrin imides 11M in good yields. These chromophores possess metallochlorin‐like optical properties. Demetalation of the NiII complex furnishes the free‐base porphyrinoid 11, which possesses a porphyrin‐like optical spectrum. The monooximes are ultimately derived from meso‐tetraphenylporphyrin, and the formal replacement of the porphyrin β,β′‐double bond by an imide functionality is thus demonstrated. The imide functionality serves as a synthetic handle for further modification of the chromophore.

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“…chlorins and porphyrins) . The incorporation of auxochromes such as phenyl, vinyl and acetyl groups at selected positions allows wavelength tuning of the strong NIR absorption band , known as the Q y band . Chart 1 shows representative free‐base (metal‐free) bacteriochlorins B1 – B11 that bear such auxochromes at the 3‐position, 13‐position or both positions.…”

Section: Introductionmentioning

confidence: 99%

Photophysical Properties and Electronic Structure of Bacteriochlorin–Chalcones with Extended Near‐Infrared Absorption

Yang

Ruzié

Krayer

et al. 2013

Photochem & Photobiology

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Synthetic bacteriochlorins enable systematic tailoring of substituents about the bacteriochlorin chromophore and thereby provide insights concerning the native bacteriochlorophylls of bacterial photosynthesis. Nine free-base bacteriochlorins (eight prepared previously and one prepared here) have been examined that bear diverse substituents at the 13- or 3,13-positions. The substituents include chalcone (3-phenylprop-2-en-1-onyl) derivatives with groups attached to the phenyl moiety, a "reverse chalcone" (3-phenyl-3-oxo-1-enyl), and extended chalcones (5-phenylpenta-2,4-dien-1-onyl, retinylidenonyl). The spectral and photophysical properties (τs, Φf, Φ(ic), Φ(isc), τT, k(f), k(ic), k(isc)) of the bacteriochlorins have been characterized. The bacteriochlorins absorb strongly in the 780-800 nm region and have fluorescence quantum yields (Φf) in the range 0.05-0.11 in toluene and dimethylsulfoxide. Light-induced electron promotions between orbitals with predominantly substituent or macrocycle character or both may give rise to some net macrocycle ↔ substituent charge-transfer character in the lowest and higher singlet excited states as indicated by density functional theory (DFT) and time-dependent DFT calculations. Such calculations indicated significant participation of molecular orbitals beyond those (HOMO - 1 to LUMO + 1) in the Gouterman four-orbital model. Taken together, the studies provide insight into the fundamental properties of bacteriochlorins and illustrate designs for tuning the spectral and photophysical features of these near-infrared-absorbing tetrapyrrole chromophores.

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De novo synthesis and photophysical characterization of annulated bacteriochlorins. Mimicking and extending the properties of bacteriochlorophylls

Cited by 40 publications

References 80 publications

Molecular Electronic Tuning of Photosensitizers to Enhance Photodynamic Therapy: Synthetic Dicyanobacteriochlorins as a Case Study

Molecular Electronic Tuning of Photosensitizers to Enhance Photodynamic Therapy: Synthetic Dicyanobacteriochlorins as a Case Study

Expansion of a Pyrrole in meso‐Tetraphenylporphyrin to a Pyrazine Imide Moiety Using a Beckmann Rearrangement

Photophysical Properties and Electronic Structure of Bacteriochlorin–Chalcones with Extended Near‐Infrared Absorption

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De novo synthesis and photophysical characterization of annulated bacteriochlorins. Mimicking and extending the properties of bacteriochlorophylls

Cited by 40 publications

References 80 publications

Molecular Electronic Tuning of Photosensitizers to Enhance Photodynamic Therapy: Synthetic Dicyanobacteriochlorins as a Case Study

Molecular Electronic Tuning of Photosensitizers to Enhance Photodynamic Therapy: Synthetic Dicyanobacteriochlorins as a Case Study

Expansion of a Pyrrole in meso‐Tetra­phenylporphyrin to a Pyrazine Imide Moiety­ Using a Beckmann Rearrangement

Photophysical Properties and Electronic Structure of Bacteriochlorin–Chalcones with Extended Near‐Infrared Absorption

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Expansion of a Pyrrole in meso‐Tetraphenylporphyrin to a Pyrazine Imide Moiety Using a Beckmann Rearrangement