title: Crystal structures and intense luminescence of tris(3-(2'-pyridyl)-pyrazolyl)borate Tb3+and Eu3+complexes with carboxylate co-ligands.
abstract: A series of brightly luminescent new mononuclear TpPyLn(An)2(H2O) (where An-= carboxylate anion, Ln = Eu or Tb and TpPy-= tris(3-(2'-pyridyl)pyrazolyl)borate) and dinuclear (TpPyLn)2pma(MeOH)2(Ln = Eu, Tb, pma4-= tetraanion of pyromellitic acid) complexes were prepared and characterized by X-ray crystallography. Within each series the compounds possess similar molecular structures, which differ only by the nature of the carboxylate anions. The quantum efficiencies for metal-centered emission of the complexes were up to 29(3)% for Eu3+and 53(5)% for the Tb3+compounds and significantly depend on the electronic structure of the additional ligand (i.e. the carboxylate). The aliphatic carboxylate compounds' luminescence quantum yields were all similar, but different from those for the aromatic ones. The complexes with trifluoroacetate and pentafluorobenzoate unexpectedly displayed lower quantum efficiencies compared to those with the corresponding non-fluorinated analogues. Energy transfer from Tb3+to Eu3+occurs in a mixture of (TpPyEu)(pma)(TbTpPy)(MeOH)2, (TpPyEu)2(pma)(MeOH)2and (TpPyTb)2(pma)(MeOH)2but is not very efficient. The Tb3+-compounds displayed green electroluminescence, and both the Eu3+and Tb3+complexes exhibited bright metal-centered red (Eu3+) or green (Tb3+) triboluminescence.
authors.affiliation: L. V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of the Ukraine, Prospekt Nauki 31, Kiev, 03028, Ukraine. shchuk@inphyschem-nas.kiev.ua.
authors.forename: Elena A
authors.initials: EA
authors.lastname: Mikhalyova
authors.affiliation: L. V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of the Ukraine, Prospekt Nauki 31, Kiev, 03028, Ukraine. shchuk@inphyschem-nas.kiev.ua.
authors.forename: Anastasiya V
authors.initials: AV
authors.lastname: Yakovenko
authors.affiliation: STARBURSTT CyberInstrumentation Consortium and Department of Chemistry, Youngstown State University, One University Plaza, Youngstown OH 44555-3663, USA and Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IN 47907, USA. zeller4@purdue.edu.
authors.forename: Matthias
authors.initials: M
authors.lastname: Zeller
authors.affiliation: Chembiocenter, Taras Shevchenko National University Of Kiev, Chervonotkatska, 61, 03022, Kiev, Ukraine.
authors.forename: Konstantin S
authors.initials: KS
authors.lastname: Gavrilenko
authors.affiliation: N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Prosp. 31, 119991 Moscow, GSP-1, Russian Federation.
authors.forename: Mikhail A
authors.initials: MA
authors.lastname: Kiskin
authors.affiliation: A.V. Bogatsky Physico-Chemical Institute of the National Academy of Sciences of the Ukraine, 86 Lustdorfskaya doroga, 65080 Odessa, Ukraine.
authors.forename: Sergey S
authors.initials: SS
authors.lastname: Smola
authors.affiliation: A.V. Bogatsky Physico-Chemical Institute of the National Academy of Sciences of the Ukraine, 86 Lustdorfskaya doroga, 65080 Odessa, Ukraine.
authors.forename: Vladimir P
authors.initials: VP
authors.lastname: Dotsenko
authors.affiliation: N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Prosp. 31, 119991 Moscow, GSP-1, Russian Federation.
authors.forename: Igor L
authors.initials: IL
authors.lastname: Eremenko
authors.affiliation: Department of Chemistry, Drexel University, Philadelphia, PA 19104-2816, USA. AddisonA@drexel.edu.
authors.forename: Anthony W
authors.identifier: http://orcid.org/0000-0002-0706-7377
authors.initials: AW
authors.lastname: Addison
authors.affiliation: L. V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of the Ukraine, Prospekt Nauki 31, Kiev, 03028, Ukraine. shchuk@inphyschem-nas.kiev.ua.
authors.forename: Vitaly V
authors.initials: VV
authors.lastname: Pavlishchuk