Guanidinium Vanadate [C(NH 2 ) 3 ] 3 VO 4 ·2H 2 O Revealing Enhanced Second-Harmonic Generation and Wide Band Gaps.

A new guanidinium-templated vanadate, [C(NH 2 ) 3 ] 3 VO 4 ·2H 2 O, has been synthesized in a phase-pure form. It crystallizes in a noncentrosymmetric polar space group, Cc , and the crystal structure is built upon a framework of guanidinium, vanadate tetrahedra, and water molecules linked by hydrogen bonds. Notably, optical measurements reveal that the material exhibits an approximately 9.6-fold enhancement in second-harmonic generation efficiency compared to its phosphate analogue. The enhancement can be attributed to the increased geometrical distortion of the VO 4 tetrahedra. Furthermore, we found that the coordination number of the central vanadium atom significantly affects the optical band gaps. Among various coordination numbers, the 4-coordinate VO 4 tetrahedra are found to be more favorable for widening the optical band gap of materials compared to the 5- and 6-coordinate vanadium polyhedra, as demonstrated by this work.