V‐Shaped Methylpyrimidinium Chromophores for Nonlinear Optics. Issue 5 (11th May 2021)

• Record Type: Journal Article
• Authors: Achelle, Sylvain; Verbitskiy, Egor V.; Fecková, Michaela; Bureš, Filip; Barsella, Alberto; Robin‐le Guen, Françoise
• Is Part Of: ChemPlusChem. Volume 86:Issue 5(2021)
• Page Start: 758
• Page End: 762
• Publication Date: 2021-05-11
• Subjects: chromophores -- donor-acceptor systems -- photophysics -- pyrimidines -- second-order nonlinear optics; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/cplu.202100081
• Languages: English
• ISSNs: 2192-6506

Abstract

Abstract: A series of four V‐shaped methylpyrimidinium salts bearing diphenylamino‐electron‐donating groups appended at various pyrimidine positions were designed. These chromophores were obtained by regioselective N(1) monomethylation by methyl methanesulfonate of the pyrimidine core. Linear optical properties were studied experimentally and electronic properties were further completed by (TD)‐DFT calculations. The second‐order nonlinear optical (NLO) properties were also studied using electric field induced second harmonic generation (EFISH) method in chloroform, and all pyrimidinium salts exhibited μβ0 >1000×10 −48 esu. The 2, 4‐disubstituted pyrimidinium core is preferred over 4, 6‐disubstitution as it enhances the NLO response and increases the dipole moment. (E, E)‐2, 4‐Bis[4‐(diphenylamino)styryl]‐1‐methylpyrimidin‐1‐ium methanesulfonate appears to be the best NLO‐phore in chloroform in the series ( μβ0 =2500×10 −48 esu) and a figure of merit μβ0 /MW=3.4 10 −48 esu mol g −1 . Abstract : A series of four diphenylamino‐substituted V‐shaped pyrimidinium methanesulfonate salt were designed and their second order nonlinear optical (NLO) properties were thoroughly studied by electric field induced second harmonic generation (EFISH). All pyrimidinium salts exhibited μβ0 >1000×10 −48 esu in chloroform. The 2, 4‐disubstituted pyrimidinium core enhances the NLO response over 4, 6‐disubstituted analogues.