Crystals of mixed alkali neodymium orthoborates, K 9 Li 3 Nd 3 (BO 3 ) 7 and A 2 LiNd(BO 3 ) 2 (A = Rb, Cs) were obtained by spontaneous crystallization. K 9 Li 3 Nd 3 (BO 3 ) 7 crystallizes in space group P2/c with cell parameters of a = 11.4524(7) Å, b = 10.1266(6) Å, c = 12.3116 (10) Å, β = 122.0090(10)°. In the structure, NdO 8 polyhedra share corners and connect with planer BO 3 groups to form infinite [Nd 3 B 3 O 21 ] n chains. These chains are linked by additional BO 3 groups to produce a double layer of [Nd 6 B 6 O 38 ] n blocks in the ac plane with K and Li ions filled into the cavities. 424 A 2 LiNd(BO 3 ) 2 (A = Rb, Cs) crystallizes in space group Pbcm, with cell parameters of a = 7.113(2) Å, b = 9.691(3) Å and c = 10.135(3) Å for Rb 2 LiNd(BO 3 ) 2 , and a = 7.2113(3) Å, b = 9.9621(4) Å, and c = 10.3347(4) Å for Cs 2 LiNd(BO 3 ) 2 . In the structure, NdO 8 polyhedra are corner-sharing with each other and further interlinked by BO 3 groups to comprise the infinite [Nd 4 B 4 O 24 ] sheets in the bc plane, with Rb/ Cs and Li ions occupying the interlayered space. The compounds show effective near-IR emission and their associated lifetimes are obtained by fluorescence spectra.La 2 CaB 10 O 19 (LCB) are explored as promising nonlinear optical (NLO) materials and their Nd 3+ -doped counterparts are also developed to be self-frequency doubling (SFD) materials [12][13][14] . Since the alkali metal ions are closed-shell electron systems, the alkali rare-earth borates usually exhibit wide transparent range and short ultraviolet absorption edge which inherits the high laser damage threshold of those crystals. Thus, considerable efforts have been made to obtain compounds in the A 2 O-RE 2 O 3 -B 2 O 3 (A = alkali) ternary systems and a number of compounds: such as Li 6 REO 90 etc. have been discovered over the past years. [15][16][17] Among them, Na 3 RE 9 O 3 (BO 3 ) 8 shows large nonlinear optical and electro-optical coefficients, and Li 6 RE(BO 3 ) 3 is proposed as an important crystal for heat-scintillation cryogenic bolometers. [18,19] However, the quaternary systems with mixed alkali cations, A 2 O-AЈ 2 O-RE 2 O 3 -B 2 O 3 , have not been extensively studied so far. Only three borate compounds with compositions of CsLiGd ) are analytically pure agents as received.
Journal of Inorganic and General ChemistryZeitschrift für anorganische und allgemeine Chemie www.zaac.wiley-vch.de
ARTICLE
Synthesis and Single-crystal Growth of K 9 Li 3 Nd 3 (BO 3 ) 7 :Raw materials were weighed according to the molar ratio of K 2 CO 3 :Li 2 CO 3 :Nd 2 O 3 :H 3 BO 3 = 6:3:1:7. The starting chemicals were ground, mixed, and fed into a platinum crucible, which was transferred to a resistance heating furnace. The crucible was kept at soaking temperature of 900°C for 24 h for exhaustive homogenization. Afterwards, the crucible was slowly cooled down to 500°C at 1.5 K·h -1 . The furnace was powered off and cooled down to room temperature. Purple transparent crystals in millimeter sizes were extracted after washed by glycerol and etha...