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© 2020 BSPD, IAPD and John Wiley Sons A/S. Published by John Wiley Sons Ltd.Smart multifunctional molecular ferroelectrics bearing high Curie temperatures and diverse excellent physical properties such as second harmonic generation (SHG) responses, luminescence, and semi-conductivity, among others, have significant applications but are seldom documented reported. Herein, by introducing the rare-earth metals Nd and Pr into a simple molecular system (( n Bu) 4 N) 3 [M(NO 3 ) x (SCN) y ] (CH 3 CH 2 CH 2 CH 2 ) 4 N = tetrabutyl ammonium, M =