A comparison of sensitized Ln(III) emission using pyridine- and pyrazine-2,6-dicarboxylates--part II.

The synthesis, X-ray structures and photophysical properties of several new Ln(III) complexes with the dianion of pyrazine-2,6-dicarboxylic acid (H(2)PYZ) that demonstrate excellent stability and solubility in non-aqueous solution are reported, and compared to structurally analogous complexes derived from pyridine-2,6-dicarboxylic acid (H(2)DPA). The Eu(III) and Yb(III) complexes demonstrate efficient metal centered luminescence in the visible and Near Infra-Red (NIR) regions, respectively. Low temperature (77 K) phosphorescence measurements using the corresponding Gd(III) complex has allowed the photophysical properties of the sensitizer to be rationalized, together with corresponding TD-DFT studies for a model complex. Lastly, we have evaluated the sensitization efficiencies for these complexes, and have undertaken femtosecond transient absorption (TA) measurements in order to evaluate the relative importance of the intersystem crossing and energy transfer processes involved with sensitized Ln(III) emission via the antennae effect.

[1]  F. Artizzu,et al.  Silica sol-gel glasses incorporating dual-luminescent Yb quinolinolato complex: processing, emission and photosensitising properties of the 'antenna' ligand. , 2012, Dalton transactions.

[2]  H. Mager,et al.  Investigations on pyrazine derivatives II. The preparation of pyrazine 2,3,5‐tricarboxylic acid and of pyrazine 2,5‐ and 2,6‐dicarboxylic acids , 2010 .

[3]  M. Kozlov,et al.  Luminescent probes for ultrasensitive detection of nucleic acids. , 2010, Bioconjugate chemistry.

[4]  B. Wardle.  Principles and Applications of Photochemistry , 2010 .

[5]  A. Nonat,et al.  Water Stability and Luminescence of Lanthanide Complexes of Tripodal Ligands Derived from 1,4,7‐Triazacyclononane: Pyridinecarboxamide versus Pyridinecarboxylate Donors , 2009 .

[6]  E. Vauthey,et al.  Excited-state dynamics of hybrid multichromophoric systems: toward an excitation wavelength control of the charge separation pathways. , 2009, The journal of physical chemistry. A.

[7]  J. Bünzli,et al.  Surprisingly bright near-infrared luminescence and short radiative lifetimes of ytterbium in hetero-binuclear Yb-Na chelates. , 2009, Inorganic chemistry.

[8]  R. Pal,et al.  A europium luminescence assay of lactate and citrate in biological fluids. , 2009, Organic & biomolecular chemistry.

[9]  Jean-Claude G Bünzli,et al.  Intrinsic quantum yields and radiative lifetimes of lanthanide tris(dipicolinates). , 2009, Physical chemistry chemical physics : PCCP.

[10]  R. Pal,et al.  Cell-penetrating metal complex optical probes: targeted and responsive systems based on lanthanide luminescence. , 2009, Accounts of chemical research.

[11]  J. Pécaut,et al.  Comparison of two tetrapodal N,O ligands: impact of the softness of the heterocyclic N-donors pyridine and pyrazine on the selectivity for Am(III) over Eu(III). , 2009, Inorganic chemistry.

[12]  Jide Xu,et al.  3-Hydroxypyridin-2-one complexes of near-infrared (NIR) emitting lanthanides: sensitization of holmium(III) and praseodymium(III) in aqueous solution. , 2008, Angewandte Chemie.

[13]  G. Angulo,et al.  Spectroscopic characteristics of a novel highly fluorescent p-phenylenediamine : Tetracyano-p-phenylenediamine , 2008 .

[14]  T. Gunnlaugsson,et al.  Solution studies of trimetallic lanthanide luminescent anion sensors: towards ratiometric sensing using an internal reference channel. , 2008, Dalton transactions.

[15]  Jide Xu,et al.  Aryl-bridged 1-hydroxypyridin-2-one: sensitizer ligands for Eu(III). , 2008, Inorganic chemistry.

[16]  S. Petoud,et al.  Azulene-moiety-based ligand for the efficient sensitization of four near-infrared luminescent lanthanide cations: Nd3+, Er3+, Tm3+, and Yb3+. , 2008, Chemistry.

[17]  E. Vauthey,et al.  Excited-state dynamics of donor-acceptor bridged systems containing a boron-dipyrromethene chromophore: interplay between charge separation and reorientational motion. , 2007, The journal of physical chemistry. A.

[18]  Xiang-Jun Zheng,et al.  Novel 3D LnIII-CuI supramolecular architecture based on 2D MOFs with (6,3) topology. , 2007, Inorganic chemistry.

[19]  Robin Taylor,et al.  Mercury: visualization and analysis of crystal structures , 2006 .

[20]  J. Bünzli,et al.  Europium and Terbium tris(Dipicolinates) as Secondary Standards for Quantum Yield Determination , 2004 .

[21]  A. Beeby,et al.  Intramolecular sensitisation of lanthanide(III) luminescence by acetophenone-containing ligands: the critical effect of para-substituents and solvent , 2002 .

[22]  J. Verhoeven,et al.  The emission spectrum and the radiative lifetime of Eu3+ in luminescent lanthanide complexes , 2002 .

[23]  S. Botchway,et al.  Luminescence imaging microscopy and lifetime mapping using kinetically stable lanthanide(III) complexes. , 2000, Journal of photochemistry and photobiology. B, Biology.

[24]  D. Reinhoudt,et al.  A Systematic Study of the Photophysical Processes in Polydentate Triphenylene-Functionalized Eu3+, Tb3+, Nd3+, Yb3+, and Er3+ Complexes , 2000 .

[25]  P. Gans,et al.  GLEE, a new computer program for glass electrode calibration. , 2000, Talanta.

[26]  Louis J. Farrugia,et al.  WinGX suite for small-molecule single-crystal crystallography , 1999 .

[27]  P. Gans,et al.  Investigation of equilibria in solution. Determination of equilibrium constants with the HYPERQUAD suite of programs. , 1996, Talanta.

[28]  J. Harrowfield,et al.  A Strongly Luminescent Organic‐Solvent‐Soluble Salt of the Tris(dipicolinato)europium(III) Trianion , 1995 .

[29]  J. Harrowfield,et al.  Synthetic, Structural, and Spectroscopic Studies on Solids Containing Tris(dipicolinato) Rare Earth Anions and Transition or Main Group Metal Cations , 1995 .

[30]  J. R. Peterson,et al.  The effects of hydration on the luminescence spectra of trisodium tris(2,6-pyridinedicarboxylato)europium(III) compounds , 1990 .

[31]  D. F. Eaton,et al.  International Union of Pure and Applied Chemistry Organic Chemistry Division Commission on Photochemistry. Reference materials for fluorescence measurement. , 1988, Journal of photochemistry and photobiology. B, Biology.

[32]  J. Buenzli,et al.  FT IR and fluorometric investigation of rare earth and metallic ion solvation. 1. Europium perchlorate in anhydrous acetonitrile , 1982 .

[33]  R. D. Shannon.  Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides , 1976 .

[34]  J. C. Lewis.  Germination of bacterial spores by calcium chelates of dipicolinic acid analogues. , 1972, The Journal of biological chemistry.

[35]  J. Demas,et al.  Measurement of photoluminescence quantum yields. Review , 1971 .

[36]  I. Grenthe.  STABILITY RELATIONSHIPS AMONG THE RARE EARTH DIPICOLINATES , 1961 .

[37]  W. Bennett,et al.  Coördination Compounds of Metal Ions with Derivatives and Analogs of Ammoniadiacetic Acid1 , 1957 .

[38]  J. Forrest.  Refractive Index Values for Potassium Bromide , 1942 .

[39]  F. Weygand.  Über N‐Glykoside, II. Mitteil.: Amadori‐Umlagerungen , 1940 .

[40]  A. Beeby,et al.  Sensitised luminescence from phenanthridine appended lanthanide complexes: analysis of triplet mediated energy transfer processes in terbium, europium and neodymium complexes , 2001 .

[41]  R. Longo,et al.  Spectroscopic properties and design of highly luminescent lanthanide coordination complexes , 2000 .

[42]  A. Beeby,et al.  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 , 1999 .

[43]  I. Yamazaki,et al.  Intramolecular electronic relaxation and photoisomerization processes in the isolated azabenzene molecules pyridine, pyrazine and pyrimidine , 1983 .

[44]  W. Horrocks,et al.  Lanthanide ion probes of structure in biology. Laser-induced luminescence decay constants provide a direct measure of the number of metal-coordinated water molecules , 1979 .