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Abstract

A new family of lanthanide/boron-based complexes have been synthesized from the novel substituted poly(pyrazolylpyridyl)borate ligand containing phenyl substituents on the boron atom Ph2Bppy (L). The complexes have been fully characterized by analytical and spectroscopic methods. The single crystal X-ray structure and mass spectroscopy reveal the isostructural dinuclear complexes: [Ln2(L)2(NO3)2(OH)2] where Ln = Eu, Gd or Tb. Upon excitation of the Ln(III) complexes in DCM, their luminescence spectra display narrow f–f transitions. It is found that the ligand can efficiently sensitize the Tb(III) complex because of the better triplet state energy match to the Tb(III)–5D0 excited states.

Keywords

Boron europium(III) terbium(III) crystal structure emission.

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References

  1. Braunschweig, H. and Colling, M. Transition metal complexes of boron — synthesis, structure and reactivity. Coordination Chemistry Reviews, 2001, 223, 1-51.
  2. Alexandrova, A.N., Boldyrev, A.I., Zhai, H.-J. and Wang, L.-S. All-boron aromatic clusters as potential new inorganic ligands and building blocks in chemistry. Coordination Chemistry Reviews, 2006, 250, 2811-2866.
  3. Grimes, R.N. Boron-carbon ring ligands in organometallic synthesis. Chemical Reviews, 1992, 92, 251-268.
  4. Braunschweig, H. and Whittell, G.R. Boron as a bridging ligand. Chemistry, European Journal, 2005, 11, 6128-6133.
  5. Trofimenko, S. Recent advances in poly(pyrazolyl)borate (scorpionate) chemistry. Chemical Reviews, 1993, 93, 943-980.
  6. Trofimenko, S. Boron-pyrazole chemistry. Journal of the American Chemical Society, 1966, 88, 1842-1844.
  7. Adams, H., Batten, S.R., Davies, G.M., Duriska, M.B., Jeffery, J.C., Jensen, P., Lu, J., Motson, G.R., Coles, S.J., Hursthouse, M.B. and Ward, M.D. New bis-, tris- and tetrakis(pyrazolyl)borate ligands with 3-pyridyl and 4-pyridyl substituents: synthesis and coordination chemistry. Dalton Transaction, 2005, 1910-1923.
  8. Curtis, M.D., Shiu, K.B, Butler, W.M. and Hauffman, J.C. Syntheses, structures, and molecular orbital analysis of hydridotris(pyrazoly1)borate (Tp) molybdenum carbonyls: Paramagnetic TpMo(CO)3 and triply bonded Tp,Mo2(CO), (Mo= Mo). Journal of the American Chemical Society,1986, 108, 3335-3343.
  9. Roundhill, S.G., Roundhill, D.M., Bloomquist, D.R., Landee, C., Willett, R.D., Dooley, D.M. and Gray, H.A. Molecular structure and magnetic properties of the chloro-bridged dimer chloro[hydrotris(1-pyrazolyl)borato]copper(II). Observation of a ferromagnetic ground state. Inorganic Chemistry, 1979, 18, 831-835.
  10. Canty, J., Minchin, N.J., Engelhardt, L.M., Skelton, B.W. and White, A.H. Interaction of palladium(II) with polydentate ligands, including the synthesis and structure of bis[tris(pyrazol-1-yl)borato-N,N′]palladium(II) and the cations [Pd(L)2]2+[L = tris(pyrazol-1-yl)methane-N,N′ or tris(pyridin-2-yl)methane-N,N′]. Dalton Transaction, 1986, 645-650.
  11. Trofimenko, S. Polypyrazolylborates: Scorpionates. Journal of Chemical Education, 2005, 82, 1715-1720.
  12. Ward, M.D., McCleverty, J.A. and Jeffery, J.C. Coordination and supramolecular chemistry of multinucleating ligands containing two or more pyrazolyl-pyridine ‘arms’. Coordination Chemistry Reviews, 2001, 222, 251-272.
  13. Psillakis, E., Jeffery, J.C., McCleverty, J.A. and Ward, M.D. A dinuclear double-helical complex of potassium ions with a compartmental bridging ligand containing two terdentate N-donor fragments. Journal of Chemical Society, Chemical Communications, 1997, 479-480.
  14. Humphrey, E.R., Mann, K.L.V., Reeves, Z.R., Behrendt, A., Jeffery, J.C., McCleverty, J.A. and Ward, M.D. Copper(II) complexes of new potentially hexadentate N3S3- or N6-donor podand ligands based on the tris(pyrazolyl)borate or tris(pyrazolyl)methane core. New Journal of Chemistry, 1999, 23, 417-427.
  15. Mann, K.L.V., Jeffery, J.C., McCleverty, J.A. and Ward, M.D. Synthesis of the new ligand bis[3-(2-pyrazinyl-pyrazol-1-yl) dihydroborate, and the crystal structures of its complexes with thallium(I) and lead(II). Polyhedron, 1999, 18, 721-727.
  16. Rheingold, A.L., Incarvito, C.D. and Trofimenko, S. Hydrotris[3-(carboxypyrrolidido)pyrazol-1-yl]borate, the first proven N3O3-hexadentate homoscorpionate ligand. Journal of Chemical Society, Dalton Transaction, 2000, 1233-1234.
  17. Paul, R.L., Amoroso, A.J., Jones, P.L., Couchman, S.M., Reeves, Z.R., Rees, L.H., Jeffery, J.C., McCleverty, J.A. and Ward, M.D. Effects of metal co-ordination geometry on self-assembly: a monomeric complex with trigonal prismatic metal co-ordination vs. tetrameric complexes with octahedral metal co-ordination. Journal of Chemical Society, Dalton Transaction, 1999, 1563-1568.
  18. Davies, G.M., Adams, H. and Ward, M.D. Bis(1,3-diphen¬ylpropane-1,3-dionato-κ2O,O′){hydro¬tris¬[3-(2-pyrid-yl)pyrazol-1-yl]borato}praseodymium(III): another member of an unpredicta¬ble series. Acta Crystallographica Section C, 2005, 61, m221-m223.
  19. Trofimenko, S. Boron-pyrazole chemistry. IV. Carbon- and boron-substituted poly[(1-pyrazolyl) borates]. Journal of American Chemical Society, 1967, 89, 6288-6294.
  20. Cotton, F.A. and Murillo, C.A. The structure of bis(diphenyldipyrazolylborato) nickel(II). Inorganica Chimica Acta, 1976, 17, 121-124.
  21. Bruce, M.I. and Walsh, J.D. Chemistry of the group 1B elements. XIII. Complexes of Copper(I) or Silver(I) containing only poly(pyrazolyl)borate ligands. Australian Journal of Chemistry, 1979, 32, 2753-2756.
  22. Fleming, J.S., Psillakis, E., Couchman, S.M., Jeffery, J.C., McCleverty, J.A. and Ward, M.D. Kinetics and thermodynamics of the reaction of peroxides with manganese-reconstituted horseradish peroxidase: a stopped-flow transient kinetic investigation. Journal of Chemical Society, Dalton Transaction, 1998, 537-544.
  23. Davies, G.M., Adams, H., Pope, S.J.A., Faulkner, S. and Ward, M.D. Photophysical properties of Pr(III) and Er(III) complexes of poly(pyrazolyl) borates. Photochemical and Photobiological Sciences, 2005, 4, 829-834.
  24. Picraux, L.B., Weldon, B.T. and McCusker, J.K. Intramolecular excimer formation in a naphthalene-appended dinuclear iron−oxo somplex. Inorganic Chemistry, 2003, 42, 273-282.
  25. Tanner, P.A. Some misconceptions concerning the electronic spectra of tri-positive europium and cerium. Chemical Society Reviews, 2013, 42, 5090-5101.
  26. Latva, M., Takalo, H. and Mukkala, V.M., Matachescu, C., Rodriguez-Ubis, J.-C. and Kankare, J. Correlation between the lowest triplet state energy level of the ligand and lanthanide(III) luminescence quantum yield. Journal of Luminescence, 1997, 75, 149-169.
  27. Sheldrick, G.M. SADABS: A program for absorption correction with the Siemens SMART system. University of Göttingen, Göttingen, Germany, 1996.
  28. Sheldrick, G.M. SHELXS-97: A program for solution of crystal structures, University of Göttingen, Göttingen, Germany, 1997.