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Synthesis and photophysical properties of chlorins bearing 0-4 distinct meso-substituents

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Abstract

The presence of substituents at designated sites about the chlorin macrocycle can alter the spectral properties, a phenomenon that can be probed through synthesis. Prior syntheses have provided access to chlorins bearing distinct aryl substituents (individually or collectively) at the 5, 10, and 15-positions, but not the 20-position. A new Western half (5-phenyl-2,3,4,5-tetrahydro-1,3,3-trimethyldipyrrin) has been employed in condensation with an Eastern half (9-bromodipyrromethane-1-carboxaldehyde) followed by oxidative cyclization to give (5% yield) the zinc(ii) 20-phenylchlorin. Condensation of the same Western half and a diaryl-substituted Eastern half provided (11% yield) the zinc(ii) 5,10,20-triarylchlorin; demetalation with TFA followed by 15-bromination and Suzuki coupling gave the free base 5,10,15,20-tetraarylchlorin. Altogether, 10 new synthetic chlorins have been prepared. The near-UV (B) absorption band of the free base chlorins shifts bathochromically from 389 to 429 nm and that for the zinc chlorins from 398 to 420 nm as the number of meso-aryl rings is increased stepwise from 0-4. The long-wavelength (Qy) absorption band undergoes a bathochromic and hypochromic shift upon increase in number of meso-aryl groups. Regardless of the number and positions of the meso-aryl substituents (including “walking a phenyl group around the ring”), the respective fluorescence quantum yields (0.17 to 0.27) and singlet excited-state lifetimes (9.4 to 13.1 ns) are comparable among the free base chlorins and the same is true for the zinc chelates (0.057 to 0.080; 1.2 to 1.6 ns). Density functional theory calculations show that of the frontier molecular orbitals of the chlorin, the energy of the HOMO−1 is the most affected by meso-aryl substituents, undergoing progressive destabilization as the number of meso-aryl groups is increased. The availability of chlorins with 0-4 distinct meso-aryl substituents provides the individual stepping-stones to bridge the known unsubstituted chlorin and the meso-tetraarylchlorins.

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Authors and Affiliations

  1. Department of Chemistry, North Carolina State University, Raleigh, NC, 27695-8204, USA

    Kunche Aravindu, Masahiko Taniguchi & Jonathan S. Lindsey

  2. Department of Science Education, Gongju National University of Education, Gongju, 314-711, Korea

    Han-Je Kim

  3. Department of Chemistry, Washington University, St. Louis, MO, 63130-4889, USA

    Preston L. Dilbeck & Dewey Holten

  4. Department of Chemistry, University of California, Riverside, CA, 92521-0403, USA

    James R. Diers & David F. Bocian

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  1. Kunche Aravindu
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  2. Han-Je Kim
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  8. Jonathan S. Lindsey
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Correspondence to Jonathan S. Lindsey.

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Electronic supplementary information (ESI) available: Synthesis of a meso-aryl-substituted Western half. See DOI: 10.1039/c3pp50240f

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Aravindu, K., Kim, HJ., Taniguchi, M. et al. Synthesis and photophysical properties of chlorins bearing 0-4 distinct meso-substituents. Photochem Photobiol Sci 12, 2089–2109 (2013). https://doi.org/10.1039/c3pp50240f

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  • DOI: https://doi.org/10.1039/c3pp50240f

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