Photophysical Characterization of the Naturally Occurring Dioxobacteriochlorin Tolyporphin A and Synthetic Oxobacteriochlorin Analogues

• Published in: Photochemistry and photobiology 2017-10, Vol.93 (5), p.1204-1215
• Main Authors: Hood, Don, Niedzwiedzki, Dariusz M., Zhang, Ran, Zhang, Yunlong, Dai, Jingqiu, Miller, Eric S., Bocian, David F., Williams, Philip G., Lindsey, Jonathan S., Holten, Dewey
• Format: Article
• Language: English
• Subjects: Absorption; Absorption spectra; Acetic acid; Bacteriochlorophyll; Chlorophyll; Cyanobacteria - chemistry; Dichloromethane; Diethyl ether; Dimethylformamide; Ethanol; Ethyl acetate; Excitation spectra; Fluorescence; Internal conversion; Methanol; Photochemistry; Porphyrins - chemistry; solar (fuels), photosynthesis (natural and artificial), biofuels (including algae and biomass), bio-inspired, charge transport, membrane, synthesis (novel materials), synthesis (self-assembly); Spectrometry, Fluorescence; Spectrophotometry, Ultraviolet; Toluene; Wavelength; X-rays
• ISSN: 0031-8655; 1751-1097
• DOI: 10.1111/php.12781

Tolyporphins are tetrapyrrole macrocycles produced by a cyanobacterium‐containing culture known as HT‐58‐2. Tolyporphins A–J are free base dioxobacteriochlorins, whereas tolyporphin K is an oxochlorin. Here, the photophysical characterization is reported of tolyporphin A and two synthetic analogues, an oxobacteriochlorin and a dioxobacteriochlorin. The characterization (in toluene, diethyl ether, ethyl acetate, dichloromethane, 1‐pentanol, 2‐butanone, ethanol, methanol, N,N‐dimethylformamide and dimethylsulfoxide) includes static absorption and fluorescence spectra, fluorescence quantum yields and time‐resolved data. The data afford the lifetime of the lowest singlet excited state and the yields of the nonradiative decay pathways (intersystem crossing and internal conversion). The three macrocycles exhibit only modest variation in spectroscopic and excited‐state photophysical parameters across the solvents. The long‐wavelength (Qy) absorption band of tolyporphin A appears at ~680 nm and is remarkably narrow (full‐width‐at‐half‐maximum ~7 nm). The position of the long‐wavelength (Qy) absorption band of tolyporphin A (~680 nm) more closely resembles that of chlorophyll a (662 nm) than bacteriochlorophyll a (772 nm). The absorption spectra of tolyporphins B–I, K (which were available in minute quantities) are also reported in methanol; the spectra of B–I closely resemble that of tolyporphin A. Taken together, tolyporphin A generally exhibits spectral and photophysical features resembling those of chlorophyll a. Tolyporphins A–J are free base dioxobacteriochlorins produced by a cyanobacterium‐containing culture. Tolyporphin A (~680 nm, fwhm ~7 nm) and an analogous synthetic dioxobacteriochlorin exhibit spectral features more closely resembling those of chlorophylls rather than bacteriochlorophylls. The spectral and photophysical features are relatively unchanged across 10 solvents of diverse polarity. The in vivo function of tolyporphins remains unknown.