A new polar alkaline earth-rare earth iodate: Ba 2 Ce(IO 3 ) 8 (H 2 O).

A new alkaline earth-rare earth iodate, Ba 2 Ce(IO 3 ) 8 (H 2 O), has been synthesised by a hydrothermal method and its structure has been determined by single-crystal X-ray diffraction. Ba 2 Ce(IO 3 ) 8 (H 2 O) crystallises in the polar space group Pna 2 1 (No. 33) with unit cell parameters of a = 15.5042(5) Å, b = 7.8841(3) Å, c = 19.5359(8) Å, V = 2388.00(15) Å 3 , and Z = 4. The structure of Ba 2 Ce(IO 3 ) 8 (H 2 O) is characterised by zero-dimensional (0D) [Ce(IO 3 ) 8 (H 2 O)] 4- units separated by Ba 2+ cations. Large crystals of Ba 2 Ce(IO 3 ) 8 (H 2 O) with dimensions of a few millimetres have been grown. The UV-vis-NIR transmission spectroscopy measurements of the compound showed that it has a short wavelength absorption edge at 381 nm. Ba 2 Ce(IO 3 ) 8 (H 2 O) exhibits a relatively weak second-harmonic-generation (SHG) response, about 0.2 times that of KDP, which is mainly due to the fact that the polarisation effects of the IO 3 groups in the structure largely cancel each other out. The relationships between the structure and the physical properties of Ba 2 Ce(IO 3 ) 8 (H 2 O) have also been calculated theoretically. Ba 2 Ce(IO 3 ) 8 (H 2 O) has a band gap of 2.44 eV, which is determined by the Ce-O and I-O interactions and is larger than those of many simple metal iodates. The introduction of alkaline earth metals favours an increase in band gap. Our work shows that the SHG and birefringence properties are closely related to the arrangement of the functional groups in the compounds.