Abstract
A series of ketocoumarin compounds were prepared as heavy atom-free triplet photosensitizers. The photophysical properties of the compounds were studied with steady state and time-resolved spectroscopy. The compounds show absorption in the visible spectral region (molar absorption coefficients are up to ε = 136 000 M−1 cm−1 at 448 nm) and long-lived triplet excited states (τT = 199.7 μs) upon visible light photoexcitation. The compounds were used as triplet photosensitizers for singlet oxygen (1O2)-mediated photooxidation of 1,5-dihydroxylnaphthalene (DHN) to produce juglone. 1O2 quantum yields of these compounds were determined in the range of 0.28–0.48. The ketocoumarins were also used as triplet photosensitizers for triplet—triplet annihilation (TTA) upconversion, and upconversion quantum yields up to 11.3% were observed. The results are useful for preparation of heavy atom-free triplet photosensitizers and for their application in photocatalysis and TTA upconversion.
Similar content being viewed by others
Notes and references
Y. Yasu, T. Koike, M. Akita, Sunlight-driven synthesis of γ-diketones via oxidative coupling of enamines with silyl enol ethers catalyzed by [Ru(bpy)3]2+, Chem. Commun., 2012, 48, 5355–5357.
M. Rueping, S. Zhu, R. M. Koenigs, Visible-light photoredox catalyzed oxidative Strecker reaction, Chem. Commun., 2011, 47, 12709–12711.
L. Shi, W. Xia, Photoredox functionalization of C–H bonds adjacent to a nitrogen atom, Chem. Soc. Rev., 2012, 41, 7687–7697.
A. Gorman, J. Killoran, C. O’Shea, T. Kenna, W. M. Gallagher, D. F. O’Shea, In vitro demonstration of the heavy-atom effect for photodynamic therapy, J. Am. Chem. Soc., 2004, 126, 10619–10631.
D. Phillips, Light relief: photochemistry and medicine, Photochem. Photobiol. Sci., 2010, 9, 1589–1596.
A. E. O’Connor, W. M. Gallagher, A. T. Byrne, Porphyrin and nonporphyrin photosensitizers in oncology: preclinical and clinical advances in photodynamic therapy, Photochem. Photobiol., 2009, 85, 1053–1074.
Y. Cakmak, S. Kolemen, S. Duman, Y. Dede, Y. Dolen, B. Kilic, Z. Kostereli, L. T. Yildirim, A. L. Dogan, D. Guc, E. U. Akkaya, Designing excited states: theory-guided access to efficient photosensitizers for photodynamic action, Angew. Chem. Int. Ed., 2011, 50, 11937–11941.
F. Schmitt, J. Freudenreich, N. P. E. Barry, L. Juillerat-Jeanneret, G. Süss-Fink, B. Therrien, Organometallic cages as vehicles for intracellular release of photosensitizers, J. Am. Chem. Soc., 2012, 134, 754–757.
J. Lalevée, M. Peter, F. Dumur, D. Gigmes, N. Blanchard, M.-A. Tehfe, F. Morlet-Savary, J. P. Fouassier, Subtle ligand effects in oxidative photocatalysis with iridium complexes: application to photopolymerization, Chem.–Eur. J., 2011, 17, 15027–15031.
J. Kim, H. Oh, E. Kim, A dual-functional monomer having an epoxy and methacrylate group for holographic recording, J. Mater. Chem., 2008, 18, 4762–4768.
T. N. Singh-Rachford, F. N. Castellano, Photon upconversion based on sensitized triplet–triplet annihilation, Coord. Chem. Rev., 2010, 254, 2560–2573.
J. Zhao, S. Ji, H. Guo, Triplet–triplet annihilation based upconversion: from triplet sensitizers and triplet acceptors to upconversion quantum yields, RSC Adv., 2011, 1, 937–950.
S. Baluschev, V. Yakutkin, T. Miteva, Y. Avlasevich, S. Chernov, S. Aleshchenkov, G. Nelles, A. Cheprakov, A. Yasuda, K. Müllen, G. Wegner, Blue-green up-conversion: noncoherent excitation by NIR light, Angew. Chem. Int. Ed., 2007, 46, 7693–7696.
A. Monguzzi, M. Frigoli, C. Larpent, R. Tubino, F. Meinardi, Low-power-photon up-conversion in dual-dye-loaded polymer nanoparticles, Adv. Funct. Mater., 2012, 22, 139–143.
G. Bergamini, P. Ceroni, P. Fabbrizi, S. Cicchi, A multichromophoric dendrimer: from synthesis to energy up-conversion in a rigid matrix, Chem. Commun., 2011, 47, 12780–12782.
Y. C. Simon, C. Weder, Low-power photon upconversion through triplet–triplet annihilation in polymers, J. Mater. Chem., 2012, 22, 20817–20830.
J. Zhao, S. Ji, W. Wu, W. Wu, H. Guo, J. Sun, H. Sun, Y. Liu, Q. Li, L. Huang, Transition metal complexes with strong absorption of visible light and long-lived triplet excited states: from molecular design to applications, RSC Adv., 2012, 2, 1712–1728.
D. B. Papkovsky, T. C. O’Riordan, Emerging applications of phosphorescent metalloporphyrins, J. Fluoresc., 2005, 15, 569–584.
N. Adarsh, R. R. Avirah, D. Ramaiah, Tuning photosensitized singlet oxygen generation efficiency of novel Aza-BODIPY dyes, Org. Lett., 2010, 12, 5720–5723.
N. Adarsh, M. Shanmugasundaram, R. R. Avirah, D. Ramaiah, Aza-BODIPY derivatives: enhanced quantum yields of triplet excited states and the generation of singlet oxygen and their role as facile sustainable photooxygenation catalysts, Chem.–Eur. J., 2012, 18, 12655–12662.
W. Wu, H. Guo, W. Wu, S. Ji, J. Zhao, Organic triplet sensitizer library derived from a single chromophore (BODIPY) with long-lived triplet excited state for triplet–triplet annihilation based upconversion, J. Org. Chem., 2011, 76, 7056–7064.
S. Guo, W. Wu, H. Guo, J. Zhao, Room temperature long-lived triplet excited states of naphthalenediimides and their applications as organic triplet photosensitizers for photooxidation and triplet–triplet annihilation upconversions, J. Org. Chem., 2012, 77, 3933–3943.
N. Turro, V. Ramamurthyand J. Scaiano, Principles of Molecular Photochemistry: An Introduction, University Science Books, Sausalito, CA, 2009.
J. P. Spechtp, E. Martic, S. Fari, Ketocoumarins: a new class of triplet sensitizers, Tetrahedron, 1982, 38, 1203–1211.
J. B. Borak, D. E. Falvey, Ketocoumarin dyes as electron mediators for visible light induced carboxylate photorelease, Photochem. Photobiol. Sci., 2010, 9, 854–860.
Y. Zhao, X. Li, F. Wu, X. Fang, Novel multi-branched two-photon polymerization initiators of ketocoumarin derivatives, J. Photochem. Photobiol., A, 2006, 177, 12–16.
P. Yang, J. Zhao, W. Wu, X. Yu, Y. Liu, Accessing the long-lived triplet excited states in bodipy-conjugated 2-(2-hydroxyphenyl) benzothiazole/benzoxazoles and applications as organic triplet photosensitizers for photooxidations, J. Org. Chem., 2012, 77, 6166–6178.
H.-C. Chen, C.-Y. Hung, K.-H. Wang, H.-L. Chen, W. S. Fann, F.-C. Chien, P. Chen, T. J. Chow, C.-P. Hsu, S.-S. Sun, White-light emission from an upconverted emission with an organic triplet sensitizer, Chem. Commun., 2009, 4064–4066.
S. Ji, W. Wu, W. Wu, H. Guo, J. Zhao, Ruthenium(ii) polyimine complexes with a long-lived 3IL excited state or a 3MLCT/3IL equilibrium: efficient triplet sensitizers for low-power upconversion, Angew. Chem. Int. Ed., 2011, 50, 1626–1629.
W. Wu, W. Wu, S. Ji, H. Guo, J. Zhao, Accessing the long-lived emissive 3IL triplet excited states of coumarin fluorophores by direct cyclometallation and its application for oxygen sensing and upconversion, Dalton Trans., 2011, 40, 5953–5963.
H. Sun, H. Guo, W. Wu, X. Liu, J. Zhao, Coumarin phosphorescence observed with N N Pt(ii) bisacetylide complex and its applications for luminescent oxygen sensing and triplet–triplet-annihilation based upconversion, Dalton Trans., 2011, 40, 7834–7841.
Y. Liu, W. Wu, J. Zhao, X. Zhang, H. Guo, Accessing the long-lived near-IR-emissive triplet excited state in naphthalenediimide with light-harvesting diimine platinum(ii) bisacetylide complex and its application for upconversion, Dalton Trans., 2011, 40, 9085–9089.
S. Ji, H. Guo, W. Wu, W. Wu, J. Zhao, Ruthenium(ii) polyimine–coumarin dyad with non-emissive 3IL excited state as sensitizer for triplet–triplet-annihilation based upconversion, Angew. Chem. Int. Ed., 2011, 50, 8283–8286.
Q. Liu, T. Yang, W. Feng, F. Li, Blue-emissive upconversion nanoparticles for low-power-excited bioimaging in vivo, J. Am. Chem. Soc., 2012, 134, 5390–5397.
Y. Y. Cheng, B. Fückel, R. W. MacQueen, T. Khoury, R. G. C. R. Clady, T. F. Schulze, N. J. Ekins-Daukes, M. J. Crossley, B. Stannowski, K. Lips, T. W. Schmidt, Improving the light-harvesting of amorphous silicon solar cells with photochemical upconversion, Energy Environ. Sci., 2012, 5, 6953–6959.
S. M. Borisov, C. Larndorfer, I. Klimant, Triplet–triplet annihilation-based anti-stokes oxygen sensing materials with a very broad dynamic range, Adv. Funct. Mater., 2012, 22, 4360–4368.
X. Yi, J. Zhao, W. Wu, D. Huang, S. Ji, J. Sun, Rhenium(i) tricarbonyl polypyridine complexes showing strong absorption of visible light and long-live triplet excited states as triplet photosensitizer for triplet–triplet annihilation upconversion, Dalton Trans., 2012, 41, 8931–8940.
C. A. Parker, Phosphorescence and delayed fluorescence from solutions, Adv. Photochem., 1964, 2, 305–383.
T. N. Singh-Rachford, F. N. Castellano, Low power visible-to-UV upconversion, J. Phys. Chem. A, 2009, 113, 5912–5917.
G. Bergamini, P. Ceroni, M. Maestri, V. Balzani, S.-K. Lee, F. Vögtle, Forward (singlet–singlet) and backward (triplet–triplet) energy transfer in a dendrimer with peripheral naphthalene units and a benzophenone core, Photochem. Photobiol. Sci., 2004, 3, 898–905.
P. Ceroni, Energy up-conversion by low-power excitation: new applications of an old concept, Chem.–Eur. J., 2011, 17, 9560–9564.
W. Wu, J. Zhao, J. Sun, S. Guo, Light harvesting fullerene dyads as organic triplet photosensitizers for triplet–triplet annihilation upconversions, J. Org. Chem., 2012, 77, 5305–5312.
P. Yang, W. Wu, J. Zhao, D. Huang, X. Yi, Using C60–bodipy dyads that show strong absorption of visible light and longlived triplet excited states as organic triplet photosensitizers for triplet–triplet annihilation upconversion, J. Mater. Chem., 2012, 22, 20273–20283.
D. Huang, J. Zhao, W. Wu, X. Yi, P. Yang, J. Ma, Visible light-harvesting triphenylamine ethynyl C60–BODIPY dyads as heavy-atom-free organic triplet photosensitizers for triplet–triplet annihilation upconversion, Asian J. Org. Chem., 2012, 1, 264–273.
S. Guo, J. Sun, L. Ma, W. You, P. Yang, J. Zhao, Visible light-harvesting naphthalenediimide (NDI)–C60 dyads as heavy-atom free organic triplet photosensitizers for triplet–triplet annihilation based upconversion, Dyes Pigm, 2013, 96, 449–458.
A. A. Rachford, S. G. Raymond Ziessel, F. N. Castellano, Ligand localized triplet excited states in platinum(ii) bipyridyl and terpyridyl peryleneacetylides, Inorg. Chem., 2008, 47, 4348–4355.
C. Zhang, J. Y. Zheng, Y. S. Zhao, J. Yao, Self-modulated white light outcoupling in doped organic nanowire waveguides via the fluctuations of singlet and triplet excitons during propagation, Adv. Mater., 2011, 23, 1380–1384.
R. R. Islangulov, D. V. Kozlov, F. N. Castellano, Low power upconversion using MLCT sensitizers, Chem. Commun., 2005, 3776–3778.
P. Du, R. Eisenberg, Energy upconversion sensitized by a platinum(ii) terpyridyl acetylide complex, Chem. Sci., 2010, 1, 502–506.
T. N. Singh-Rachford, F. N. Castellano, Supra-nanosecond dynamics of a red-to-blue photon upconversion system, Inorg. Chem., 2009, 48, 2541–2548.
T. N. Singh-Rachford, A. Nayak, M. L. Muro-Small, S. Goeb, M. J. Therien, F. N. Castellano, Supermolecular-chromophore-sensitized near-infrared-to-visible photon upconversion, J. Am. Chem. Soc., 2010, 132, 14203–14211.
A. Monguzzi, R. Tubino, S. Hoseinkhani, M. Campione, F. Meinard, Low power, non-coherent sensitized photon up-conversion: modelling and perspectives, Phys. Chem. Chem. Phys., 2012, 14, 4322–4332.
W. Wu, J. Sun, S. Ji, W. Wu, J. Zhao, H. Guo, Tuning the emissive triplet excited states of platinum(ii) Schiff base complexes with pyrene, and application for luminescent oxygen sensing and triplet–triplet-annihilation based upconversions, Dalton Trans., 2011, 40, 11550–11561.
W. Wu, H. Guo, W. Wu, S. Ji, J. Zhao, Long-lived room temperature deep-red/near-IR emissive intraligand triplet excited state (3IL) of naphthalimide in cyclometalated Pt(ii) complexes and its application in upconversion, Inorg. Chem., 2011, 50, 11446–11460.
W. Wu, J. Zhao, H. Guo, J. Sun, S. Ji, Z. Wang, Long-lived room temperature near-IR phosphorescence of BODIPY in a visible light-harvesting N C N PtII acetylide complex with directly metalated BODIPY chromophore, Chem.–Eur. J., 2012, 18, 1961–1968.
Q. Li, H. Guo, L. Ma, W. Wu, Y. Liu, J. Zhao, Tuning the photophysical properties of N N Pt(ii) bisacetylide complexes with fluorene moiety and its applications for triplet–triplet-annihilation based upconversion, J. Mater. Chem., 2012, 22, 5319–5329.
W. Wu, S. Ji, W. Wu, J. Shao, H. Guo, T. D. James, J. Zhao, Ruthenium(ii) polyimine–coumarin light harvesting molecular arrays: design rationales and application for triplet–triplet annihilation based upconversion, Chem.–Eur. J., 2012, 18, 4953–4964.
Y. Chen, J. Zhao, L. Xie, H. Guo, Q. Li, Thienyl-substituted BODIPYs with strong visible light-absorption and long lived triplet excited states as organic triplet sensitizers for triplet–triplet annihilation upconversion, RSC Adv., 2012, 2, 3942–3953.
J. Sun, W. Wu, J. Zhao, Long-lived room temperature deep-red emissive intraligand triplet excited state of naphthalimide in cyclometalated Ir(iii) complexes and its application in triplet–triplet annihilation based upconversion, Chem.–Eur. J., 2012, 18, 8100–8112.
W. Wu, J. Zhao, J. Sun, L. Huang, X. Yi, Red-light excitable fluorescent platinum(ii) bis(aryleneethynylene) bis(trialkylphosphine) complexes showing long-lived triplet excited states as triplet photosensitizers for triplet–triplet annihilation upconversion, J. Mater. Chem. C, 2013, 1, 705–716.
X. Yi, J. Zhao, J. Sun, S. Guo, H. Zhang, Visible light-absorbing rhenium(i) tricarbonyl complexes as triplet photosensitizers in photooxidation and triplet–triplet annihilation upconversion, Dalton Trans., 2013, 42, 2062–2074.
Sk. Jasimuddin, T. Yamada, K. Fukuju, J. Otsuki, K. Sakai, Photocatalytic hydrogen production from water in self-assembled supramolecular iridium–cobalt systems, Chem. Commun., 2010, 46, 8466–8468.
W.-G. Wang, F. Wang, H.-Y. Wang, C.-H. Tung, L.-Z. Wu, Electron transfer and hydrogen generation from a molecular dyad: platinum(ii) alkynyl complex anchored to [FeFe] hydrogenase subsite mimic, Dalton Trans., 2012, 41, 2420–2426.
F. Gärtner, D. Cozzula, S. Losse, A. Boddien, G. Anilkumar, H. Junge, T. Schulz, N. Marquet, A. Spannenberg, S. Gladiali, M. Beller, Synthesis, characterisation and application of iridium(iii) photosensitisers for catalytic water reduction, Chem.–Eur. J., 2011, 17, 6998–7006.
G. Zhao, C. Yang, L. Guo, H. Sun, C. Chen, W. Xia, Visible light-induced oxidative coupling reaction: easy access to Mannich-type products, Chem. Commun., 2012, 48, 2337–2339.
J. Xuan, W.-J. Xiao, Visible-light photoredox catalysis, Angew. Chem. Int. Ed., 2012, 51, 6828–6838.
A. A. Abdel-Shafi, J. L. Bourdelande, S. S. Ali, Photosensitized generation of singlet oxygen from rhenium(i) and iridium(iii) complexes, Dalton Trans., 2007, 2510–2516.
R. B. P. Elmes, M. Erby, S. M. Cloonan, S. J. Quinn, D. C. Williams, T. Gunnlaugsson, Quaternarized pdppz: synthesis, DNA-binding and biological studies of a novel dppz derivative that causes cellular death upon light irradiation, Chem. Commun., 2011, 47, 686–688.
A. Kamkaew, S. H. Lim, H. B. Lee, L. V. Kiew, L. Y. Chung, K. Burgess, BODIPY dyes in photodynamic therapy, Chem. Soc. Rev., 2013, 42, 77–88.
S. G. Awuah, Y. You, Boron dipyrromethene (BODIPY)-based photosensitizers for photodynamic therapy, RSC Adv., 2012, 2, 11169–11183.
S.-y. Takizawa, R. Aboshi, S. Murata, Photooxidation of 1,5-dihydroxynaphthalene with iridium complexes as singlet oxygen sensitizers, Photochem. Photobiol. Sci., 2011, 10, 895–903.
J. Benites, J. A. Valderrama, K. Bettega, R. C. Pedrosa, P. Buc Calderon, J. Verrax, Biological evaluation of donor–acceptor aminonaphthoquinones as antitumor agents, Eur. J. Med. Chem., 2010, 45, 6052–6057.
W. Wu, P. Yang, L. Ma, J. Lalevée, J. Zhao, Visible-light harvesting PtII complexes as singlet oxygen photosensitizers for photooxidation of 1,5-dihydroxynaphthalene, Eur. J. Inorg. Chem., 2013, 2, 228–231.
J. Sun, J. Zhao, H. Guo, W. Wu, Visible-light harvesting iridium complexes as singlet oxygen sensitizers for photooxidation of 1,5-dihydroxynaphthalene, Chem. Commun., 2012, 48, 4169–4171.
L. Huang, X. Yu, W. Wu, J. Zhao, Styryl Bodipy–C60 dyads as efficient heavy-atom-free organic triplet photosensitizers, Org. Lett., 2012, 14, 2594–2957.
Author information
Authors and Affiliations
Corresponding author
Additional information
Electronic supplementary information (ESI) available: Synthesis details and more spectra. See DOI: 10.1039/c3pp25416j
Rights and permissions
About this article
Cite this article
Huang, D., Sun, J., Ma, L. et al. Preparation of ketocoumarins as heavy atom-free triplet photosensitizers for triplet—triplet annihilation upconversio. Photochem Photobiol Sci 12, 872–882 (2013). https://doi.org/10.1039/c3pp25416j
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1039/c3pp25416j