Abstract
The new non‐centrosymmetric tin fluoride borate Sn3[B3O7]F was synthesized hydrothermally, and was characterized by single‐crystal and powder X‐ray diffraction, vibrational spectroscopy, DFT calculations, second harmonic generation (SHG) measurements, thermogravimetry, and differential scanning calorimetry. Its SHG response is about 12 times that of quartz. The compound crystallizes in the non‐centrosymmetric orthorhombic space group Pna21 with lattice parameters a=922.4(2), b=769.8(4), and c=1221.9(6) pm (Z=4). Characteristic for the structure are isolated B3O7 moieties, consisting of two corner‐sharing BO3 units and one BO4 tetrahedron. These occupy half of the octahedral voids of a slightly distorted hexagonal closest packing of Sn2+ atoms, with [SnF]+ units in the other half of the octahedral voids. Sn3[B3O7]F is transparent over a wide spectral range with a UV cut‐off edge at about 263 nm.
Highlights
At the beginning of the 1960s, shortly after the demonstration of the first laser, Franken et al.[1] observed for the first time second harmonic generation (SHG) when illuminating a quartz crystal with a ruby laser
Sn3[B3O7]F is the first compound in the system Sn-B-O-F, which was synthesized by a straightforward, cost-efficient hydrothermal synthesis
The Sn2 cations and the F anions are located in a row with the B3O7 units
Summary
Borates are of great interest as NLO materials as the boron atom in borates possesses the ability to coordinate either three or four oxygen atoms to form trigonal planar [BO3]3À or tetrahedral [BO4]5À units These building units within a chiral structure adopt a coplanar configuration to promote SHG and birefringence. Further fluoride borates include Pb3B6O11F2,[12] Ba3B6O11F2,[13] Cd5(BO3)3F,[14] and the fluorooxoborates BiB2O4F,[15] NaB4O6F,[16] SrB5O7F3,[17] CsB4O6F[18] have been reported, which show SHG All these compounds were synthesized using high-temperature synthesis methods, with Pb3B6O11F2 being an exception as it was produced under hydrothermal conditions at 240 8C.
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