Crystals of Fe3R(BO3)4 (R = Y, La, Nd) have been grown. Their structure and properties show close relations. The structures of these materials have been established by single-crystal X-ray diffraction. They crystallize in the huntite, CaMg3(CO3)4, structure type, trigonal system, space group R32 (No. 155), Z = 3, with unit-cell parameters (Å) a = 9.592(1), 9.578(1), and 9.563(2) and c = 7.597(7), 7.605(3), and 7.575(2), for R = La, Nd, and Y0.5Bi0.5, respectively. They contain RO6 trigonal prisms and smaller FeO6 octahedra forming layers and giving rise to Fe−R distances of ≃3.78 Å. RO6 polyhedra are interconnected within the layers by corner sharing with triangular BO3 groups of two types and FeO6 octahedra. FeO6 octahedra form 1D helicoidal chains with relatively short Fe−Fe distances, ≃3.18 Å. The temperature dependence of the magnetic susceptibility from 350 to 1.8 K for Fe3R(BO3)4 shows two maxima at about 260 and 35 K and, for R = Nd, another maximum at 6 K. The presence of magnetic order is attributed to magnetic Fe−Fe or Fe−O−Fe interactions. Infrared spectra in the range 4000−240 cm-1 show the ν1, ν3, and ν4 IR-active bands of the B(1)O3 3- triangular groups as well as ν2 of less symmetrical B(2)O3 3-.

A comparison of the suitability of two Tm 3+ -doped monoclinic double tungstate KRE(WO 4 ) 2 (RE = Gd 3+ or Lu 3+ ) laser crystals was carried out based on crystal growth conditions and the strength of crystal field interactions provided by the corresponding host at the Tm 3+ site. For the same 3% Tm 3+ substitution level, macrodefect-free single crystals can be grown, with higher cooling rates and lower temperatures for the KLu(WO 4 ) 2 host. Furthermore, the information provided by the phenomenological crystal field analysis of low temperature polarized spectroscopic data for both hosts indicates that KLu(WO 4 ) 2 exhibits the stronger crystal field and thus an enhanced 3 H 6 splitting compared to KGd(WO 4 ) 2 . Considering these factors as well as its calculated higher emission cross sections, it is concluded that KLu(WO 4 ) 2 is the most suitable of the two hosts for Tm 3+ doping.

Single crystals of Yb 3+ -doped NaGd͑WO 4 ͒ 2 with up to 20 mol % ytterbium content have been grown by the Czochralski technique in air or in N 2 +O 2 atmosphere and cooled to room temperature at different rates ͑4-250°C/h͒. Only the noncentrosymmetric tetragonal space group I4 accounts for all reflections observed in the single crystal x-ray diffraction analysis. The distortion of this symmetry with respect to the centrosymmetric tetragonal space group I4 1 / a is much lower for crystals cooled at a fast rate. Na + , Gd 3+ , and Yb 3+ ions share the two nonequivalent 2b and 2d sites of the I4 structure, but Yb 3+ ͑and Gd 3+ ͒ ions are found preferentially in the 2b site. Optical spectroscopy at low ͑5 K͒ temperature provides additional evidence of the existence of these two sites contributing to the line broadening. The comparison with the 2 F 7/2 ͑n͒ and 2 F 5/2 ͑nЈ͒ Stark energy levels calculated using the crystallographic Yb-O bond distances allows to correlate the experimental optical bands with the 2b and 2d sites. As a novel uniaxial laser host for Yb 3+ , NaGd͑WO 4 ͒ 2 is characterized also with respect to its transparency, band-edge, refractive indices, and main optical phonons. Continuous-wave Yb 3+ -laser operation is studied at room temperature both under Ti:sapphire and diode laser pumping. A maximum slope efficiency of 77% with respect to the absorbed power is achieved for the polarization by Ti:sapphire laser pumping in a three-mirror cavity with Brewster geometry. The emission is tunable in the 1014-1079 nm spectral range with an intracavity Lyot filter. Passive mode locking of this laser produces 120 fs long pulses at 1037.5 nm with an average power of 360 mW at Ϸ97 MHz repetition rate. Using uncoated samples of Yb: NaGd͑WO 4 ͒ 2 at normal incidence in simple two-mirror cavities, output powers as high as 1.45 W and slope efficiencies as high as 51% are achieved with different diode laser pump sources.

No abstract

NaBi(WO 4 ) 2 (NBW), NaBi(MoO 4 ) 2 (NBMo) and LiBi(MoO 4 ) 2 (LBMo) single crystals grown by the Czochralski technique have been doped up to a praseodymium concentration of [Pr] ≈ 1 × 10 20 cm −3 in the crystal. 10 K polarized optical absorption and photoluminescence measurements have been used to determine the energy position of 32, 39 and 36 Pr 3+ Stark levels in NBW, NBMo and LBMo crystals, respectively. These energy levels were labelled with the appropriate irreducible representations corresponding to a C 2 local symmetry of an average optical centre. Single-electron Hamiltonians including free-ion and crystal field interactions have been used in the fitting of experimental energy levels and in the simulation of the full sequence of the 4f 2 Pr 3+ configuration. 300 K absorption spectra of different 2S+1 L J Pr 3+ multiplets were determined and used in the context of the Judd-Ofelt theory and for the calculation of the 1 D 2 -related emission cross sections of this average Pr 3+ centre. Non-radiative electron relaxation from the 3 P 0 level feeds the 1 D 2 multiplet. This latter level efficiently decays radiatively to the ground 3 H 4 multiplet but still there is a significant rate of radiative decay to the 1 D 2 → 3 F 3 praseodymium laser channel. For [Pr] 2 × 10 19 cm −3 , non-radiative electric dipole-dipole Pr pair energy transfer limits the radiative yield.

A new zeolite-type structure is adopted by (NH(4))(+)[M(NH(3))(2)](+)(Ge(9)O(19))(2-) (M=Cu, Ag; shown in the picture). These compounds are the first microporous germanates containing a transition metal complex inside their tunnels. The large separation between the metal centers and the unhindered access of reactants to these active sites through uniformly sized channels make these materials a good point of departure for designing new catalysts.

The polarized optical absorption (OA) and photoluminescence of Pr3+ doped KGd(WO4)2 (KGW) single crystals have been measured at selected temperatures between 7 and 300 K. For the studied Pr concentrations, [Pr] = 0.03×1020-1.9×1020 cm-3, a unique site is observed. 74 energy levels were experimentally determined for this site and labelled with the appropriate A or B irreducible representations corresponding to the C2 symmetry of the Gd point site in KGW. The set was fitted to a Hamiltonian of adjustable parameters including free-ion as well as real Bqk and complex Sqk crystal-field parameters. A good simulation of the experimental crystal field energies was achieved with a root mean square deviation σ = 15.3 cm-1. Distortions in the oxygen bonds to Pr3+ are found to contribute to the broadening of some OA bands, particularly those related to the 1D2 multiplet. The OA edge is determined by the interconfigurational 4f→4f15d1 Pr3+ transition peaking at 34 200 cm-1. From the average 300 K OA cross sections the radiative lifetimes of the Pr3+ multiplets have been calculated considering the standard and modified Judd-Ofelt (JO) theories. A better agreement with the experimental results is obtained by the standard theory: the average JO parameters obtained at ω̄2 = 12.0×10-20 cm2, ω̄4 = 8.15×10-20 cm2 and ω̄6 = 2.64×10-20 cm2. Electrons excited to the 3P0 multiplet decay very efficiently to the 1D2 multiplet even at 15 K. In samples with [Pr]⩾0.3×1020 cm-3 the excitation of the 1D2 multiplet decays non-radiatively by an electric dipole-dipole transfer between Pr neighbours.

Eight 2D and 3D metal-organic framework (MOF) rare earth naphthalenedisulfonates have been obtained. The different geometry of the naphthalenedisulfonic acids used as connectors [(1,5-NDS) and (2,6-NDS)] gives rise to the three new structure types. In Ln(OH)(1,5-NDS)H2O, LnPF-1 (lanthanide polymeric framework; Ln=La, Nd, Pr, Sm and Eu), the lanthanide ion is octacoordinated. Its 3D structure is formed by (Ln2O14)-S-(Ln2O14) infinite chains, connected through complete NDS connectors. LnPF-2 (Ln=Nd), with the same empirical formula as the former, and the lanthanide in octa- and nonacoordination, owns an arrangement of sulfonate bridges and neodymium polyhedra that gives rise to a 2D structure. [Ln5(2,6-NDS)3(OH)9(H2O)4](H2O)2, LnPF-3 (Ln=Nd, Eu), demonstrates that it is possible to obtain a 3D structure with (2,6-NDS), when a greater Ln/connector ratio is employed. It is worth pointing out the existence, in this latter family of compounds, of a mu5-OH group, whose hydrogen atom is very close to one-sixth Ln atom (distance Ln...H=2.09 A). The materials, with high thermal stability, act as active and selective bifunctional heterogeneous catalysts in oxidation of linalool yielding cyclic hydroxy ethers. The absence of any 3D Nd-Nd magnetic interaction is explained due to the inner nature of 4f orbitals of Nd3+, which do not favor the magnetic exchange. The influence of the polymeric frame matrix results in a better photoluminescence efficiency for NdPF-1.