Large second-order optical nonlinearities of s-triazine derivatives: View from micro molecules to ma

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Three s-triazine derivatives have been synthesized and their structures been de-termined. These are Compound I: 2,4-dimethyl-6-(p-N,N-dimethylaminostyryl)-s-triazine (abbre-viated to NMe-1), Compound II: 2,4-dimethyl-6-(p-N,N-diethylaminostyryl)-s-triazine (to NEt-1), and Compound III: 2-methyl-4,6-bis(p-N,N-dimethylaminostyryl)-s-triazine (NMe-2). NMe-1 and NEt-1 molecules belong to the D-π-A type with a one-dimensional charge-transfer character. NMe-1 crystallizes to centrosymmetric P1 space group, while NEt-1 to non-centrosymmetric polar Cc space group with all of the molecular charge-transfer axes taking the same orientation. Under the irradiation of 1064 nm fundamental laser, NEt-1 powder crystals radiate a 2-order harmonic light with an intensity 46.8 times that of urea. The Λ typed NMe-2 molecule, which has a two-dimensional charge-transfer character, crystallizes to polar P21 space group. Its powder crystals exhibit a 2-order harmonic intensity 46.2 times that of urea. The quantum chemical cal-culations and tensor analyses have been carried out to reveal the dependence of the macro 2-order nonlinear optical (NLO) efficiency on the micro 2-order NLO coefficients (β) and on the crystalline packing styles. Three s-triazine derivatives have been synthesized and their structures have been de-termined. These are Compound I: 2,4-dimethyl-6- (pN, N-dimethylaminostyryl) -s- triazine (abbre- viated to NMe-1) Compound II: 2,4-dimethyl-6- (pN, N-diethylaminostyryl) -s-triazine (to NEt- NMe-1 and NEt-1 molecules belong to the D-π-A type with one-dimensional charge-transfer character. NMe-1 crystallizes to centrosymmetric P1 space group, while NEt-1 to non-centrosymmetric polar Cc space group with all of the molecular charge-transfer axes taking the same orientation. Under the irradiation of 1064 nm fundamental laser, NEt-1 powder crystals radiate a 2-order harmonic light with an intensity of 46.8 times that of urea. The Λ typed NMe-2 molecule, which has a two-dimensional charge-transfer character, crystallizes to polar P21 space group. Its powder crystals exhibit a 2-order harmonic intensity 46.2 times that of urea. The qu antum chemical cal-culations and tensor analyzes have been carried out to reveal the dependence of the macro 2-order nonlinear optical (NLO) efficiency on the micro 2-order NLO coefficients (β) and on the crystalline packing styles.
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