Abstract
Transient absorption and time resolved luminescence spectroscopy were used to study photophysical processes in the macrocycle-appended 1,8-naphthalimide compound H3L, and its Eu(iii) and Gd(iii) complexes Eu·L and Gd·L, in particular the naphthalimide-Eu(iii) energy-transfer process. In all cases aggregation of the naphthalimide chromophores results in a low-energy emission feature in the 470–500 nm region in addition to the naphthalimide fluorescence; this lower-energy emission has a lifetime longer by an order of magnitude than the monomer naphthalimide fluorescence. Transient absorption spectroscopy was used to measure the decay of the naphthalimide triplet excited state, which occurs in the range 30–50 μs. In Eu·L, partial energy-transfer from the naphthalimide chromophore results in sensitized Eu(iii)-based emission in addition to the naphthalimide-based fluorescence features. Time-resolved measurements on the sensitized Eu(iii)-based emission reveal both fast (~109 s−1) and slow (~104 s−1) energy-transfer processes from the naphthalimide energy-donor, which we ascribe to energy-transfer occurring from the singlet and triplet excited state of naphthalimide respectively. This is an unusual case of observation of sensitization of Eu(iii)-based emission from the singlet state of an aromatic chromophore.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
J.-C. G. Bünzli Lanthanide luminescence for biomedical analyses and imaging Chem. Rev. 2010 110 2729
E. Eliseeva and J.-C. G. Bünzli Lanthanide luminescence for functional materials and biosciences Chem. Soc. Rev. 2010 39 189
A. Thibon and V. C., Pierre, Principles of responsive lanthanide-based luminescent probes Anal. Bioanal. Chem. 2009 394 107
D., Parker, Critical design factors for optical imaging with metal coordination complexes Aust. J. Chem. 2011 64 239
C. Allain and S., Faulkner, Photo-physical approaches to responsive optical probes Future Med. Chem. 2010 2 339
J.-C. G. Bünzli Lanthanide luminescent bioprobes Chem. Lett. 2009 104
E. J. New, D. Parker, D. G. Smith and J. W., Walton, Development of responsive lanthanide probes for cellular applications Curr. Opin. Chem. Biol. 2010 14 238
H. Uh and S., Petoud, Novel antennae for the sensitization of near infrared luminescent lanthanide cations C. R. Chim. 2010 13 668
A. K. Hagan and T., Zuchner, Lanthanide-based time-resolved luminescence immunoassays Anal. Bioanal. Chem. 2011 400 2847
E. G. Moore, A. P. S. Samuel and K. N., Raymond, From antenna to assay; lessons learned in lanthanide luminescence Acc. Chem. Res. 2009 42 542
R. Carr, N. H. Evans and D., Parker, Lanthanide complexes as chiral probes exploiting circularly polarized luminescence Chem. Soc. Rev. 2012 41 7673
M. L. Cable, D. J. Levine, J. P. Kirby, H. B. Gray and A., Ponce, Luminescent lanthanide sensors Adv. Inorg. Chem. 2011 63 1
J.-C. G. Bünzli and S., Eliseeva, Lanthanide NIR luminescence for telecommunications, bioanalyses and solar energy conversion J. Rare Earths 2010 28 824
L. D. Carlos, R. A. S. Ferreira, V. S. Bermudez, B. Julian-Lopez and P., Escribano, Progress on lanthanide-based organic-inorganic hybrid phosphors Chem. Soc. Rev. 2011 40 536
N. T. Kalyani and S. J., Dhoble, Organic light emitting diodes: energy saving lighting technology - a review Renewable Sustainable Energy Rev. 2012 16 2696
R. C. Evans, P. Douglas and C. J., Winscom, Coordination complexes exhibiting room-temperature phosphorescence: evaluation of their suitability as triplet emitters for light-emitting diodes Coord. Chem. Rev. 2006 250 2093
N. Sabbatini, M. Guardigli, J.-M. Lehn Luminescent lanthanide complexes as photochemical supramolecular devices Coord. Chem. Rev. 1993 123 201
P. Coppo, M. Duati, V. Kozhevnikov, J. W. Hofstraat and L. De Cola White-light emission from an assembly comprising luminescent iridium and europium complexes Angew. Chem., Int. Ed. 2005 44 1806
D. Sykes, I. S. Tidmarsh, A. Barbieri, I. V. Sazanovich, J. A. Weinstein and M. D., Ward, d-f Energy-transfer in a series of Ir(iii)/Eu(iii) dyads: energy-transfer mechanisms and white-light emission Inorg. Chem. 2011 50 11323
A. H. Shelton, I. V. Sazanovich, J. A. Weinstein and M. D., Ward, Controllable three-component luminescence from a 1,8-naphthalimide/Eu(iii) complex: white light emission from a single molecule Chem. Commun. 2012 48 2749
V. Wintgens, P. Valat, J. Kossanyi, L. Biczok, A. Demeter and T. Bérces Spectroscopic properties of aromatic dicarboximides. Part 1. N-H and N-methyl-substituted naphthalimides J. Chem. Soc., Faraday Trans. 1994 90 411
M. de Sousa, M. Kluciar, S. Abad, M. A. Miranda, B. de Castro and U., Pischel, An inhibit (INH) molecular logic gate based on 1,8-naphthalimide-sensitised europium luminescence Photochem. Photobiol. Sci. 2004 3 639
J. P. Cross, M. Lauz, P. D. Badger and S. Pétoud Polymetallic lanthanide complexes with PAMAM-naphthalimide dendritic ligands: luminescent lanthanide complexes formed in solution J. Am. Chem. Soc. 2004 126 16278
Z. Xu, J. Yoon and D. R., Spring, A selective and ratiometric Cu2+ fluorescent probe based on naphthalimide excimer-monomer switching Chem. Commun. 2010 46 2563
T. C. Barros, P. B. Filho, V. G. Toscano and M. J., Politi, Intramolecular excimer formation from 1,8-N-alkyldinaphthalimides J. Photochem. Photobiol. A: Chem. 1995 89 141
D. W. Cho, M. Fujitsuka, A. Sugimoto and T., Majima, Intramolecular excimer formation and photoinduced electron-transfer process in bis-1,8-naphthalimide dyads depending on the linker length J. Phys. Chem. A 2008 112 7208
W. H., Melhuish, Quantum efficiencies of fluorescence of organic substances: effect of solvent and concentration of the fluorescent solute J. Phys. Chem. 1961 65 229
W. R. Dawson and M. W., Wind, Fluorescence yields of aromatic compounds J. Phys. Chem. 1968 72 3251
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski and D. J. Fox, GAUSSIAN 09 (Revision C.02), Gaussian, Inc., Wallingford, CT, 2009
A. D., Becke, Density-functional thermochemistry. III. The role of exact exchange J. Chem. Phys. 1993 98 5648
A. Nicklass, M. Dolg, H. Stoll and H., Preuss, Ab initio energy-adjusted pseudopotentials for the noble gases Ne through Xe: calculation of atomic dipole and quadrupole polarizabilities J. Chem. Phys. 1995 102 8942
X. Y. Cao and M., Dolg, Valence basis sets for relativistic energy-consistent small-core lanthanide pseudopotentials J. Chem. Phys. 2001 115 7348, and references therein
T. H. Dunning Jr. and P. J. Hay, Gaussian basis sets for molecular calculations, in Modern Theoretical Chemistry, ed. H. F. Schaefer III, Plenum, New York, 1977, vol. 3, p. 1
C. S. Grange, A. J. H. M. Meijer and M. D., Ward, Trinuclear ruthenium dioxolene complexes based on the bridging ligand hexahydroxytriphenylene: electrochemistry, spectroscopy, and near-infrared electrochromic behaviour associated with a reversible seven-membered redox chain Dalton Trans. 2010 39 200
J.-M. Herrera, S. J. A. Pope, A. J. H. M. Meijer, T. L. Easun, H. Adams, W. Z. Alsindi, M. W. George and M. D., Ward, Photophysical and structural properties of cyanoruthenate complexes of hexaaza-triphenylene J. Am. Chem. Soc. 2007 129 11491
B. Menucci and J., Tomassi, Continuum solvation models: a new approach to the problem of solute’s charge distribution and cavity boundaries J. Chem. Phys. 1997 106 5151
M. Cossi, V. Barone, B. Mennucci and J., Tomasi, Ab initio study of ionic solutions by a polarizable continuum dielectric model Chem. Phys. Lett. 1998 286 253 and references therein
L. J. Charbonnière, S. Faulkner, C. Platas-Iglesias, M. Regueiro-Figueroa, A. Nonat, T. Rodríguez-Blas, A. de Blas, W. S. Perry and M., Tropiano, Ln2M complexes (M = Ru, Re) derived from a bismacrocyclic ligand containing a 4,4′-dimethyl-2,2′-bipyridyl bridging unit Dalton Trans. 2013 42 3667
R. Dennington, T. Keith and J. Millam, GaussView, Version 5, Semichem Inc., Shawnee Mission, KS, 2009
F. Würthner, T. E. Kaiser and C. R. Saha-Möller J-Aggregates: from serendipitous discovery to supramolecular engineering of functional dye materials Angew. Chem., Int. Ed. 2011 50 3376
M. G. Kuzmin, N. A. Sadovskii, J. A. Weinstein and O. I., Kutsenok, Exciplex mechanism of fluorescence quenching in polar media Proc. - Indian Acad. Sci., Chem. Sci. 1993 105 637
J. B. Birks and L. G., Christophorou, Excimer formation in polycyclic hydrocarbons and their derivatives Nature 1963 197 1064
G. F. de Sá, O. L. Malta, C. de Mello Donegá, A. M. Simas, R. L. Longo, P. A. Santa-Cruz and E. F. da Silva Jr. Spectroscopic properties and design of highly luminescent lanthanide coordination complexes Coord. Chem. Rev. 2000 196 165
F. R. Gonçalves e Silva, O. L. Malta, C. Reinhard, H.-U. Güdel, C. Piguet, J. E. Moser and J.-C. G. Bünzli Visible and near-infrared luminescence of lanthanide-containing dimetallic triple-stranded helicates: energy transfer mechanisms in the SmIII and YbIII molecular edifices J. Phys. Chem. A 2002 106 1670
J.-P. Malval, S. Suzuki, F. Morlet-Savary, X. Allonas, J.-P. Fouassier, S. Takahara and T., Yamaoka, Photochemistry of naphthalimide photoacid generators J. Phys. Chem. A 2008 112 3879
G. A. Hebbink, A. I. Klink, L. Grave, P. G. B. Oude Alink and F. C. J. M. van Veggel Singlet energy transfer as the main pathway in the sensitization of near-infrared Nd3+ luminescence by dansyl and lissamine dyes ChemPhysChem 2002 3 1014
A. Guenet, F. Eckes, V. Bulach, C. A. Strassert, L. De Cola and M. W., Hosseini, Sensitisation of the near-infrared emission of NdIII from the singlet state of porphyrins bearing four 8-hydroxyquinolinylamide chelates ChemPhysChem 2012 13 3163
T. L. Easun, W. Z. Alsindi, N. Deppermann, M. Towrie, K. L. Ronayne, X.-Z. Sun, M. D. Ward and M. W., George, A luminescence and time-resolved infrared study of dyads containing (diimine)Ru(4,4′-diethylamido-2,2′-bipyridine)2 and (diimine)Ru(CN)4 moieties: solvent-induced reversal of the direction of photoinduced energy-transfer Inorg. Chem. 2009 48 8759
T. L. Easun, W. Z. Alsindi, M. Towrie, K. L. Ronayne, X.-Z. Sun, M. D. Ward and M. W., George, Photoinduced energy-transfer in a conformationally flexible Re(i)/Ru(ii) dyad probed by time-resolved infra-red spectroscopy: effects of conformation and spatial localisation of excited states Inorg. Chem. 2008 47 5071
S. J. A. Pope, C. R. Rice, M. D. Ward, A. F. Morales, G. Accorsi, N. Armaroli and F., Barigelletti, Folding of a poly(oxyethylene) chain as probed by photoinduced energy transfer between Ru-and Os-polypyridine termini J. Chem. Soc., Dalton Trans. 2001 2228
M. Frank, M. Nieger, F. Vögtle, P. Belser, A. von Zelewsky, L. De Cola, V. Balzani, F. Barigeletti and L., Flamigni, Dinuclear Ru(ii) and/or Os(ii) complexes of bis-bipyridine bridging ligands containing adamantane spacers: synthesis, luminescence properties, intercomponent energy and electron transfer processes Inorg. Chim. Acta 1996 242 281
D., Parker, Luminescent lanthanide sensors for pH, pO2 and selected anions Coord. Chem. Rev. 2000 205 109
R. M. Supkowski and W. D., Horrocks, On the determination of the number of water molecules, q, coordinated to europium(iii) ions in solution from luminescence decay lifetimes Inorg. Chim. Acta 2002 340 44
Author information
Authors and Affiliations
Corresponding authors
Additional information
Electronic supplementary information (ESI) available. See DOI: 10.1039/c3pp50109d
Rights and permissions
This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.
About this article
Cite this article
Plyusnin, V.F., Kupryakov, A.S., Grivin, V.P. et al. Photophysics of 1,8-naphthalimide/Ln(iii) dyads (Ln = Eu, Gd): naphthalimide → Eu(iii) energy-transfer from both singlet and triplet states. Photochem Photobiol Sci 12, 1666–1679 (2013). https://doi.org/10.1039/c3pp50109d
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1039/c3pp50109d