Abstract. KGd(WO 4 ) 2 single crystals doped with Er 3+ have been grown by the flux top-seeded-solution growth method. The crystallographic structure of the lattice has been refined, being the lattice constants a = 10.652(4), b = 10.374(6), c = 7.582(2) Å, β = 130.80(2)• . The refractive index dispersion of the host has been measured in the 350-1500 nm range. The optical absorption and photoluminescence properties of Er The technological interest in the development of solidstate lasers for application in long-distance optical communications has promoted the study of laser ions with an emission close to the minimum of the optical losses in silica fibers, namely 1.5 µm. The present development of a new laser generation requires us to find crystals with low excitation threshold and suited to be excited by the emission of diode lasers. Er 3+ only has weak absorption bands in the 600-1000 nm region, but its photoluminescence can be sensitised by energy transfer from Yb 3+ , which shows a strong optical absorption in the 900-1000 nm range. This region overlaps the emission of InGaAs diode lasers. As a matter of fact, InGaAs diodepumped room-temperature laser operation has been recently demonstrated in KGd(WO 4 ) 2 :Yb:Er crystals [7] (hereafter KGd(WO 4 ) 2 is abbreviated as KGW), however the efficiency of the process was weak and the physical processes involved were poorly understood. Moreover, Er has been used to sensitise the Tm 3+ emission in KGW crystals at liquid nitrogen temperature [8].Despite the relevance of the optical properties of Er 3+ in KGW crystals, its spectroscopic properties have been reported at 77 K only for the 4 S 3/2 or lower energy levels [9,10]. The present work reports a spectroscopic study of the Er 3+ ions incorporated in KGW crystals grown by the flux top-seeded-solution growth (TSSG) technique.KGW crystals have been also used as a laser host for Nd 3+ ions because of the high efficiency of the 4 F 3/2 → 4 I 11/2 transition [11,12] as well as a host for other rare-earth laser ions [8]. Recently, some research has focused attention on crystals with relevant cubic nonlinearity χ (3) because with these materials it is possible to obtain unconventional lasers, such as lasers with stimulated-Raman-scattering (SRS) frequency self-conversion. The KGW:Nd possesses an effective cubic nonlinearity of about 10 −13 esu and presents a good efficiency in the process of SRS self-conversion [13].In view of the relevance of the KGW lattice host, we have also performed a refinement of the crystal structure, in order to improve the currently known lattice constants and to help in the discussion of the local lattice site symmetry when required. Further, we discuss the orientation of the indicatrix of the crystal with regards to the crystallographic axes and we have obtained the value of the refractive indices in a wide spectral region.

The crystal structure of monoclinic KGd(WO4)2 (KGW) has been refined at room temperature by using single‐crystal X‐ray diffraction data. The unit‐cell parameters are a = 10.652 (4), b = 10.374 (6), c = 7.582 (2) Å, β = 130.80 (2)°, with Z = 4, in space group C2/c. The linear thermal expansion tensor has been determined and the principal axes are [302], [010] and [106]. The principal axis with maximum thermal expansion ( = 23.44 × 10−6 K−1), , was located 12° from the c axis. Undoped crystals of KGW and crystals that were partially doped by Pr, Nd, Ho, Er, Tm and Yb were grown by the top‐seeding‐solution growth slow‐cooling method. The effect of doping on the KGW structure was observed in the cell parameters and in morphological changes. The changes in parameters follow the changes in lanthanide ionic radii. The doped crystals show {021} and {21} faces in addition to the {110}, {11}, {010}, {130} and {310} faces which basically follow the habit of the undoped KGW crystals. The development of the faces is related to the number of the most important periodic bond chains parallel to them.

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A series of new 1,2-bis(o-haloaryl)ethanones is efficiently prepared and applied to the synthesis of 4,5-bis(o-haloaryl)isoxazoles. Isolation of intermediate hydroxyisoxazolines, which are structurally examined, provides a definitive proof for a heterocyclization mechanism based on an amine exchange process. The isolation and X-ray crystallographic studies of significant side products such as benzamides and triarylpropionitriles are also described.