Abstract
Fluorescent lanthanide complexes were synthesized using a non-phenolic analog of curcumin as the principal chromophoric chelating ligand. Sensitized, near-infrared fluorescence is observed in these complexes as a result of photo-excitation of the chromophoric ligands, population of the molecular triplet state, and transfer of energy to the emitting lanthanide ion. For the purpose of intra-molecular energy transfer, the triplet states of curcuminoid ligands are more favorably matched with the excited electronic states of neodymium and ytterbium ions than those associated with less conjugated β-diketonate ligands. Sensitization of fluorescence through an internal redox reaction, thought to occur in other ytterbium complexes, is predicted to be less probable under the present circumstances.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
C. Turro, P. K.-L. Fu, and P. M. Bradley (2002). In A. Sigel and H. Sigel (Eds.), The Lanthanides and Their Interrelations with Biosystems. Vol. 40: Met. Ions Biol. Syst., Marcel Dekker, New York, pp. 323–349.
J. Kido and Y. Okamoto (2002). Organo lanthanide metal complexes for electroluminescent materials. Chem. Rev. 102, 2357–2368.
G. A. Crosby, R. E. Whan, and R. M. Alire (1961). Intramolecular energy transfer in rare earth chelates. Role of the triplet state. J. Chem. Phys. 34, 743–748.
M. Latva, H. Takalo, V. M. Mukkala, C. Matachescu, J. C. Rodríguez-Ubis, and J. Kankare (1997). Correlation between the lowest triplet state energy level of the ligand and lanthanide(III) luminescence quantum yield. J. Lumin. 75, 149–169.
M. H. V. Werts, J. W. Hofstrat, F. A. J. Geurts, and J. W. Verhoeven (1997). Fluorescein and eosin as sensitizing chromophores in near-infrared luminescent ytterbium(III), neodymium(III), and erbium(III) chelates. Chem. Phys. Lett. 276, 196–201.
A. I. Voloshin, N. M. Shavaleev, and V. P. Kazakov (2001). Mono-thio-β-diketones—A new type of ligands suitable for sensitization of lanthanide luminescence. Infrared luminescence of intensely colored neodymium and ytterbium mono-thio-β-diketone chelates. J. Lumin. 93, 115–118.
A. Beeby, R. S. Dickins, S. FitzGerald, L. J. Govenlock, C. L. Maupin, D. Parker, J. P. Riehl, G. Siligardi, and J. A. G. Williams (2000). Porphyrin sensitization of circularly polarized near-IR lanthanide luminescence: enhanced emission with nucleic acid binding. Chem. Commun. 1183–1184.
T. J. Foley, B. S. Harrison, A. S. Knefely, K. A. Abboud, J. R. Reynolds, K. S. Schanze, and J. M. Boncella (2003). Facile preparation and photophysics of near-infrared luminescent lanthanide(III) monoporphyrinate complexes. Inorg. Chem. 42, 5023–5032.
F. J. Steemers, W. Verboom, J. W. Hofstraat, F. A. J. Geurts, and D. N. Reinhoudt (1998). Near-infrared luminescence of Yb3+, Nd3+, and Er3+. Azatriphenylene complexes. Tetrahedron Lett. 39, 583– 7586.
J. W. Hofstraat, M. P. Oude Wolbers, F. C. J. M. van Veggel, D. N. Reinhoudt, M. H. V. Werts, and J. W. Verhoeven (1998). Near-IR luminescent rare earth ion-sensitizer complexes. J. Fluoresc. 8, 301–308.
S. V. Shevchuk, N. V. Rusakova, A. M. Turianskaya, Y. V. Korovin, N. A. Nazarenko, and A. I. Gren (1998). Infrared luminescence of ytterbium ion complexes with calyx[4]resorcinarenes. J. Fluoresc. 8, 225–228.
S. Faulkner, A. Beeby, R. S. Dickins, D. Parker, and J. A. Gareth Williams (1999). Generating a warm glow: Lanthanide complexes which luminescence in the near-IR. J. Fluoresc. 9, 45–49.
G. A., Hebbink, S. I. Klink, P. G. B. Oude Alink, and F. C. J. M. van Veggel (2001). Visible and near-infrared light emitting calyx[4]arene-based ternary lanthanide complexes. Inorg. Chim. Acta 317, 114–120.
N. M. Shavaleev, S. J. A. Pope, Z. R. Bell, S. Faulkner, and M. D. Ward (2003). Visible-light sensitization of near-infrared luminescence from Yb(III), Nd(III), and Er(III) complexes of 3,6-bis(2-pyridyl)tetrazine. Dalton Trans. 808–814.
G. A. Crosby and M. Kasha (1958). Intramolecular energy transfer in ytterbium organic chelates. Spectrochim. Acta 10, 377–382.
S. I. Klink, G. A., Hebbink, L. Grave, F. G. A. Peters, F. C. J. M. van Veggel, D. N. Reinhoudt, and J. W. Hofstraat (2000). Near-infrared and visible luminescence from terphenyl-based lanthanide(III) complexes bearing amido and sulfonamido pendant arms. Eur. J. Org. Chem. 10, 1923–1931.
W. D. Horrocks, J. P. Bolender, W. D. Smith, and R. M. Supkowski (1997). Photosensitized near-infrared luminescence of ytterbium(III) in proteins and complexes occurs via an internal redox process. J. Am. Chem. Soc. 119, 5972–5973.
R. M. Supkowski, J. P. Bolender, W. D. Smith, L. E. L. Reynolds, and W. D. Horrocks (1999). Lanthanide ions as redox probes of long-range electron transfer in proteins. Coord. Chem. Rev. 185–186, 307–319.
A. Beeby, R. S. Dickins, S. Faulkner, D. Parker, and J. A. G. Williams (1997). Luminescence from ytterbium(III) and its complexes in solution. Chem. Commun. 1401–1402.
A. Beeby, S. Faulkner, D. Parker, and J. A. G. Williams (2001). Sensitized luminescence from phenanthridine appended lanthanide complexes: Analysis of triplet mediated energy transfer processes in terbium, europium, and neodymium complexes. J. Chem. Soc. Perkin Trans. 2, 1268–1273.
F. Ortica and M. A. J. Rodgers (2001). A laser flash photolysis study of curcumin in dioxane-water mixtures. Photochem. Photobiol. 74, 745.
P. H. Bong (2000). Spectral and photophysical behaviors of curcumin and curcuminoids. Bull. Korean Chem. Soc. 21, 81–86.
G. S. Spicer and J. D. H. Strickland (1958). The determination of microgram and sub-microgram amounts of boron. Part I. Absorptiometric determination using curcumin. Anal. Chim. Acta 18, 231–235.
K. Krishnankutty and V. D. John (2002). Anti-tumour studies of metal chelates of synthetic curcuminoids. J. Exp. Clin. Res. 21, 219–224.
M. H. Krackov and H. E. Bellis (1997). US Patent 5,679,864, Process for the synthesis of curcumin-related compounds.
A. Sundaryono, A. Nourmamode, C. Gardrat, A. Fritsch, and A. Castellan (2003). Synthesis and complexation properties of two new curcuminoid molecules bearing a diphenylmethane linkage. J. Mol. Struct. 649, 177–190.
A. Sundaryono, A. Nourmamode, C. Gardrat, S. Grelier, G. Bravic, D. Chasseau, and A. Castellan (2003). Photochem. Photobiol. Sci. 2, 914–920.
Beeby, I. M. Clarkson, R. S. Dickins, S. Faulkner, D. Parker, L. Royle, A. S. de Sousa, J. A. G. Williams, and M. Woods (1999). Non-radiative deactivation of the excited states of europium, terbium, and ytterbium complexes by proximate energy-matched OH, NH, and CH oscillators: An improved luminescence method for establishing solution hydration states. J. Chem. Soc. Perkin Trans. 2, 493–504.
Y. Hasegawa, M. Miratsu, and G. R. Choppin (2001). Dehydration from tris[β-diketonato] lanthanoids(III) on the 1,10-phenanthroline adduct formation across lanthanoid series. Anal. Chim. Acta 428, 149–154.
F. Dietze, A. F. Arrieta, and U. Zimmer (1997). pKa stability constants and UV/VIS spectral behaviour of selected curcumin analogues. Pharmazie 52, 302–306
W. G. Perkins and G. A. Crosby (1965). Crystal-field splitting in Yb3+ chelates. J. Chem. Phys. 42, 407–411.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Seltzer, M.D., Fallis, S., Hollins, R.A. et al. Curcuminoid Ligands for Sensitization of Near-Infrared Lanthanide Emission. J Fluoresc 15, 597–603 (2005). https://doi.org/10.1007/s10895-005-2832-8
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/s10895-005-2832-8