@article{faries_diers_springer_yang_ptaszek_lahaye_krayer_taniguchi_kirmaier_lindsey_et al._2015, title={Photophysical Properties and Electronic Structure of Chlorin-Imides: Bridging the Gap between Chlorins and Bacteriochlorins}, volume={119}, ISSN={["1520-5207"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-84934319596&partnerID=MN8TOARS}, DOI={10.1021/jp511257w}, abstractNote={Efficient light harvesting for molecular-based solar-conversion systems requires absorbers that span the photon-rich red and near-infrared (NIR) regions of the solar spectrum. Reported herein are the photophysical properties of a set of six chlorin-imides and nine synthetic chlorin analogues that extend the absorption deeper (624-714 nm) into these key spectral regions. These absorbers help bridge the gap between typical chlorins and bacteriochlorins. The new compounds have high fluorescence quantum yields (0.15-0.34) and long singlet excited-state lifetimes (4.2-10.9 ns). The bathochromic shift in Qy absorption is driven by substituent-based stabilization of the lowest unoccupied molecular orbital, with the largest shifts for chlorins that bear an electron-withdrawing, conjugative group at the 3-position in combination with a 13,15-imide ring.}, number={24}, journal={JOURNAL OF PHYSICAL CHEMISTRY B}, author={Faries, Kaitlm M. and Diers, James R. and Springer, Joseph W. and Yang, Eunkyung and Ptaszek, Marcin and Lahaye, Dorothee and Krayer, Michael and Taniguchi, Masahiko and Kirmaier, Christine and Lindsey, Jonathan S. and et al.}, year={2015}, month={Jun}, pages={7503–7515} }
 @article{ptaszek_lahaye_krayer_muthiah_lindsey_2010, title={De Novo Synthesis of Long-Wavelength Absorbing Chlorin-13,15-dicarboximides}, volume={75}, ISSN={["1520-6904"]}, DOI={10.1021/jo902649d}, abstractNote={Chlorins bearing a six-membered imide ring spanning positions 13-15, commonly referred to as purpurinimides, exhibit long-wavelength absorption yet have heretofore only been available via semisynthesis from naturally occurring chlorophylls. A concise route to synthetic chlorins, which bear a geminal dimethyl group in the pyrroline ring, has been extended to provide access to chlorin-13,15-dicarboximides. The new route entails (i) synthesis of a 13-bromochlorin, (ii) palladium-catalyzed carbamoylation at the 13-position, (iii) regioselective 15-bromination under acidic conditions, and (iv) one-flask palladium-mediated carbonylation and ring closure to form the imide. In some cases the ring closure reaction afforded the isomeric (and readily separable) chlorin-isoimide in addition to the chlorin-imide. The resulting chlorin-imides and chlorin-isoimides exhibit long-wavelength absorption (679-715 nm) and emission (683-720 nm) in the far-red and near-infrared spectral region. The absorption of the chlorin-(iso)imides fills the spectral window between that of analogous synthetic chlorins and 13(1)-oxophorbines (603-687 nm) and bacteriochlorins (707-792 nm). The synthetic versatility of the de novo route complements the existing semisynthetic route from chlorophylls and should enable fundamental spectroscopic studies and photochemical applications.}, number={5}, journal={JOURNAL OF ORGANIC CHEMISTRY}, author={Ptaszek, Marcin and Lahaye, Dorothee and Krayer, Michael and Muthiah, Chinnasamy and Lindsey, Jonathan S.}, year={2010}, month={Mar}, pages={1659–1673} }
 @article{muthiah_lahaye_taniguchi_ptaszek_lindsey_2009, title={Regioselective Bromination Tactics in the de Novo Synthesis of Chlorophyll b Analogues}, volume={74}, ISSN={["0022-3263"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-66449131206&partnerID=MN8TOARS}, DOI={10.1021/jo9002954}, abstractNote={The ability to introduce substituents at designated sites about the perimeter of the chlorin or 13(1)-oxophorbine macrocycle is essential for fundamental studies related to chlorophylls. A chlorin is a dihydroporphyrin, whereas a 13(1)-oxophorbine is a chlorin containing an annulated oxopentano ring spanning positions 13 and 15. 13(1)-Oxophorbines bearing auxochromes at the 7-position of the macrocycle are valuable targets given their resemblance to chlorophyll a or b, which contains the 13(1)-oxophorbine skeleton and bears a 7-methyl or 7-formyl group, respectively. A rational route to 7-substituted 13(1)-oxophorbines was developed that relies on a new method for regioselective bromination. Under neutral conditions, a 13-acetyl-10-mesitylchlorin (FbC-M(10)A(13)) undergoes bromination (with 1 molar equiv of NBS in THF) both in ring B (7-position) and at the 15-position (42% versus 28% isolated yield), thereby thwarting installation of the isocyclic ring (ring E, spanning the 13-15 positions). Under acidic conditions (10% TFA in CH(2)Cl(2)), ring B is deactivated, and bromination occurs preferentially at the 15-position (87% yield). The capability for preferential 15-bromination is essential to install the isocyclic ring, after which bromination can be directed to the 7-position of ring B (neutral conditions, 86% yield). The ability to suppress bromination in ring B (under acidic media) has been exploited in syntheses of sparsely substituted analogues of chlorophyll b. The analogues contain a 7-substituent (acetyl, formyl, or TIPS-ethynyl), a 10-mesityl group, and the 18,18-dimethyl group as the only substituents in the 13(1)-oxophorbine skeleton. The three analogues exhibit absorption spectral features that closely resemble those of free base analogues of chlorophyll b. Taken together, the facile access to chlorins and 13(1)-oxophorbines bearing substituents at distinct sites should enable fundamental spectroscopic studies and diverse applications.}, number={9}, journal={JOURNAL OF ORGANIC CHEMISTRY}, publisher={American Chemical Society (ACS)}, author={Muthiah, Chinnasamy and Lahaye, Dorothee and Taniguchi, Masahiko and Ptaszek, Marcin and Lindsey, Jonathan S.}, year={2009}, month={May}, pages={3237–3247} }
 @misc{lahaye_muthukumaran_hung_gryko_reboucas_spasojevic_batinic-haberle_lindsey_2007, title={Design and synthesis of manganese porphyrins with tailored lipophilicity: Investigation of redox properties and superoxide dismutase activity}, volume={15}, ISSN={["1464-3391"]}, DOI={10.1016/j.bmc.2007.07.015}, abstractNote={Thirteen new manganese porphyrins and two porphodimethenes bearing one to three different substituents at the meso positions in a variety of architectures have been synthesized. The substituents employed generally are (i) electron-withdrawing to tune the reduction potential to the desirable range (near +0.3 V vs NHE), and/or (ii) lipophilic to target the interior of lipid bilayer membranes and/or the blood–brain barrier. The influence of the substituents on the MnIII/MnII reduction potentials has been characterized, and the superoxide dismutase activity of the compounds has been examined.}, number={22}, journal={BIOORGANIC & MEDICINAL CHEMISTRY}, author={Lahaye, Dorothee and Muthukumaran, Kannan and Hung, Chen-Hsiung and Gryko, Dorota and Reboucas, Julio S. and Spasojevic, Ivan and Batinic-Haberle, Ines and Lindsey, Jonathan S.}, year={2007}, month={Nov}, pages={7066–7086} }