title: Features of spectral properties of Sm(3+) complexes with dithia- and diselenophosphinate ligands.
abstract: The samarium complexes Sm(S2PPh2)3(THF)2 (1) and Sm(Se2PPh2)3(THF)2 (2) with soft-donor dithia- and diselenophosphinate ligands were synthesized and their photophysical properties were studied in detail. Both complexes displayed the metal-centered photoluminescence (PL) in visible and NIR regions corresponding to (4)G5/2→(6)HJ (J=5/2, 7/2, 9/2, 11/2, 13/2, 15/2), (6)FJ (J=1/2, 3/2, 5/2, 7/2, 9/2, 11/2) f-f transitions of Sm(3+). Luminescence decay curves exhibit an initial short build-up region and can be described by double or triple exponential function owing to multiphonon relaxation from the (4)F3/2 energy level to the (4)G5/2 one and reversible energy transfer from the Sm(3+) excited states to the triplet ((3)T1) state of phosphinate ligand. A Judd-Ofelt analysis was performed to estimate PL quantum efficiency (QE), branching ratios (β) and induced-emission cross section (σem) of the compounds obtained. It was found that the Judd-Ofelt parameter Ω2 of 1 is significantly greater than that of 2. This feature is responsible for large values of β (50.98%) and σem (4.29×10(-21)cm(2)) which suggest 1 as a good candidate for the development of samarium doped polymethylmethacrylate (PMMA) laser medium acting on the (4)G5/2→(6)H9/2 transition at 645nm. The estimated room-temperature PL QE of 1 and 2 equals to 1.9 and 0.17%, respectively.
authors.affiliation: G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Tropinina 49, 603950 Nizhny Novgorod, Russian Federation. Electronic address: pushkarev@iomc.ras.ru.
authors.forename: A P
authors.initials: AP
authors.lastname: Pushkarev
authors.affiliation: Nizhny Novgorod State University, Gagarina avenue 23/2, 603950 Nizhny Novgorod, Russian Federation; Institute for Physics of Microstructures of Russian Academy of Sciences, 7 ul. Akademicheskaya, 603950 Nizhny Novgorod, Russian Federation.
authors.forename: A N
authors.initials: AN
authors.lastname: Yablonskiy
authors.affiliation: Nizhny Novgorod State University, Gagarina avenue 23/2, 603950 Nizhny Novgorod, Russian Federation; Institute for Physics of Microstructures of Russian Academy of Sciences, 7 ul. Akademicheskaya, 603950 Nizhny Novgorod, Russian Federation.
authors.forename: P A
authors.initials: PA
authors.lastname: Yunin
authors.affiliation: G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Tropinina 49, 603950 Nizhny Novgorod, Russian Federation; Nizhny Novgorod State University, Gagarina avenue 23/2, 603950 Nizhny Novgorod, Russian Federation.
authors.forename: M E
authors.initials: ME
authors.lastname: Burin
authors.affiliation: Nizhny Novgorod State University, Gagarina avenue 23/2, 603950 Nizhny Novgorod, Russian Federation; Institute for Physics of Microstructures of Russian Academy of Sciences, 7 ul. Akademicheskaya, 603950 Nizhny Novgorod, Russian Federation.
authors.forename: B A
authors.initials: BA
authors.lastname: Andreev
authors.affiliation: G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Tropinina 49, 603950 Nizhny Novgorod, Russian Federation; Nizhny Novgorod State University, Gagarina avenue 23/2, 603950 Nizhny Novgorod, Russian Federation.
authors.forename: M N
authors.initials: MN
authors.lastname: Bochkarev
keywords: Judd–Ofelt analysis; Luminescence; Sm3+ complex; Soft-donor ligand