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Integration of Cyanine, Merocyanine and Styryl Dye Motifs with Synthetic Bacteriochlorins
Author(s) -
Yang Eunkyung,
Zhang Nuonuo,
Krayer Michael,
Taniguchi Masahiko,
Diers James R.,
Kirmaier Christine,
Lindsey Jonathan S.,
Bocian David F.,
Holten Dewey
Publication year - 2015
Publication title -
photochemistry and photobiology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.818
H-Index - 131
eISSN - 1751-1097
pISSN - 0031-8655
DOI - 10.1111/php.12547
Subject(s) - cyanine , merocyanine , chemistry , excited state , fluorescence , absorption spectroscopy , photochemistry , spectroscopy , pyridinium , stokes shift , absorption (acoustics) , materials science , photochromism , atomic physics , medicinal chemistry , physics , quantum mechanics , composite material
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 Q y 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 Q y absorption and fluorescence features with large peak separation (Stokes shift), low fluorescence yields, and shortened S 1 ( Q y ) excited‐state lifetimes (~700 ps and ~100 ps). More typical spectra and S 1 lifetime (~2.3 ns) are found for B‐3. The combined photophysical and molecular‐orbital characteristics suggest the altered spectra and enhanced nonradiative S 1 decay of B‐1 and B‐2 derive from excited‐state configurations in which electron density is shifted between the macrocycle and the substituents.