Rational design of hybrid pseudo halogenometallate salts using quasi- spherical phosphonium cations Rishukumar Panday, Ramamoorthy Boomishankar Indian Institute of Science Education and Research (IISER), Pune, India Designing of molecular ferroelectrics is a challenging task as it is difficult to predict, which moiety of the system is directing the molecule to crystallize in the noncentrosymmetric structure. Recently, molecular ferroelectrics are getting more attention because of their lightweight, easy, and environmentally friendly synthesis and easy modification in the structure, owing to certain limitations posed by ceramic-based systems. 1 Here, by using the “quasi-spherical theory” we have successfully synthesized a family of two-component ferroelectrics of formula [Ph 3 PR] x [M II/III (NCS) y ] (R = Et, Pr; x = 2, 3 and y = 4, 5, 6) supported by heteroleptic phosphonium cations. While the previously reported complexes of formula [N(Et 4 )] 3 [M(NCS) 6 ] (where, M = Mn, Fe) have crystallized in the centrosymmetric space group, the phosphonium-based compounds reported here have adopted a noncentrosymmetric structure. These observations clearly suggest that a reduction in the cation symmetry from T d to C 3v have resulted in a symmetry breaking to yield polar systems suitable for ferroelectric behavior. Their noncentrosymmetric structure was confirmed by the observation of a sharp peak in the second harmonic generation (SHG) experiment with an efficiency of 24.0 and 22.6, respectively when probed at λ pump = 1350 nm. References 1. Wei, Z.-H.; Jiang, Z.-T.; Zhang, X.-X.; Li, M.-L.; Tang, Y.-Y.; Chen, X.-G.; Cai, H.; Xiong, R.-G., Rational design of ceramic- like molecular ferroelectric by quasi-spherical theory. J. Am. Chem. Soc. 2020, 142 (4), 1995-2000.
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