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Title: Synthesis and Spectral Properties of meso-Arylbacteriochlorins, Including Insights into Essential Motifs of their Hydrodipyrrin Precursors

Synthetic bacteriochlorins—analogues of bacteriochlorophylls, Nature’s near-infrared absorbers—are attractive for diverse photochemical studies. meso-Arylbacteriochlorins have been prepared by the self-condensation of a dihydrodipyrrin–carbinol or dihydrodipyrrin–acetal following an Eastern-Western (E-W) or Northern-Southern (N-S) joining process. The bacteriochlorins bear a gem-dimethyl group in each pyrroline ring to ensure stability toward oxidation. The two routes differ in the location of the gem-dimethyl group at the respective 3- or 2-position in the dihydrodipyrrin, and the method of synthesis of the dihydrodipyrrin. Treatment of a known 3,3-dimethyldihydrodipyrrin-1-carboxaldehyde with an aryl Grignard reagent afforded the dihydrodipyrrin-1-(aryl)carbinol, and upon subsequent acetylation, the corresponding dihydrodipyrrin-1-methyl acetate (dihydrodipyrrin– acetate). Self-condensation of the dihydrodipyrrin–acetate gave a meso-diarylbacteriochlorin (E-W route). A 2,2-dimethyl-5-aryldihydrodipyrrin-1-(aryl)carbinol underwent self-condensation to give a trans-A 2B 2-type meso-tetraarylbacteriochlorin (N-S route). In each case, the aromatization process entails a 2e -/2H + (aerobic) dehydrogenative oxidation following the dihydrodipyrrin self-condensation. Comparison of a tetrahydrodipyrrin–acetal (0%) versus a dihydrodipyrrin–acetal (41%) in bacteriochlorin formation and results with various 1-substituted dihydrodipyrrins revealed the importance of resonance stabilization of the reactive hydrodipyrrin intermediate. Altogether 10 new dihydrodipyrrins and five new bacteriochlorins have been prepared. The bacteriochlorins exhibit characteristic bacteriochlorophyll-like absorption spectra, including a Q y band in the region 726–743 nm.
Authors:
 [1] ;  [1] ;  [2] ;  [1] ;  [1] ;  [1]
  1. North Carolina State Univ., Raleigh, NC (United States). Department of Chemistry
  2. Gongju National University of Education (Korea). Department of Science Education
Publication Date:
Grant/Contract Number:
FG02-05ER15651
Type:
Accepted Manuscript
Journal Name:
Molecules
Additional Journal Information:
Journal Volume: 22; Journal Issue: 4; Journal ID: ISSN 1420-3049
Publisher:
MDPI
Research Org:
Univ. of North Carolina, Chapel Hill, NC (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; self-condensation; bacteriochlorophyll; near-infrared; tetrahydrodipyrrin; dihydrodipyrrin; absorption; fluorescence; oxocarbenium ion; resonance; oxidation
OSTI Identifier:
1429912