Автореферат (1150068), страница 2

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ɉɨɬɟɧɰɢɚɥɷɬɨɣɫɢɫɬɟɦɵ ɫɨɫɬɚɜɥɹɟɬɦɢɧɭɫ ȼ ɨɬɧɨɫɢɬɟɥɶɧɨ ɫɬɚɧɞɚɪɬɧɨɝɨ ɜɨɞɧɨɝɨ ɷɥɟɤɬɪɨɞɚAg/AgCl/KClɧɚɫȾɚɥɟɟɜɫɟɩɨɬɟɧɰɢɚɥɵɞɚɧɵɨɬɧɨɫɢɬɟɥɶɧɨɨɩɢɫɚɧɧɨɝɨɜɵɲɟ ɛɟɡɜɨɞɧɨɝɨ ɷɥɟɤɬɪɨɞɚ ɫɪɚɜɧɟɧɢɹ Ɇɨɪɮɨɥɨɝɢɹ ɩɨɥɢɦɟɪɨɜɨɩɪɟɞɟɥɹɥɚɫɶ ɦɟɬɨɞɨɦ ɫɤɚɧɢɪɭɸɳɟɣ ɷɥɟɤɬɪɨɧɧɨɣ ɦɢɤɪɨɫɤɨɩɢɢɋɗɆ ɚ ɢɯ ɩɥɨɬɧɨɫɬɶ – ɮɥɨɬɚɰɢɨɧɧɵɦ ɦɟɬɨɞɨɦ ɬɟ ɩɨɭɫɬɚɧɨɜɥɟɧɢɸ ɮɥɨɬɚɰɢɨɧɧɨɝɨ ɪɚɜɧɨɜɟɫɢɹ ɦɟɠɞɭ ɤɪɭɩɢɧɤɚɦɢɩɨɥɢɦɟɪɚ ɢ ɫɦɟɫɶɸ ɠɢɞɤɨɫɬɟɣ ɪɚɡɧɨɣ ɩɥɨɬɧɨɫɬɢ ɜ ɞɚɧɧɨɣ ɪɚɛɨɬɟɨɪɬɨ-ɤɫɢɥɨɥɚ ɢ ɣɨɞɢɫɬɨɝɨ ɦɟɬɢɥɟɧɚ. Ⱦɥɹ ɢɡɭɱɟɧɢɹ ɩɪɨɞɭɤɬɨɜɞɟɫɬɪɭɤɰɢɢ ɢɡɭɱɚɟɦɵɯ ɤɨɦɩɥɟɤɫɨɜ ɢɫɩɨɥɶɡɨɜɚɥɫɹ ɦɟɬɨɞ ɦɚɬɪɢɱɧɨɚɤɬɢɜɢɪɨɜɚɧɧɨɣɥɚɡɟɪɧɨɣɞɟɫɨɪɛɰɢɢɢɨɧɢɡɚɰɢɢɆȺɅȾɂ).Ƚɥɚɜɚ ɫɨɞɟɪɠɢɬɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɟɪɟɡɭɥɶɬɚɬɵɪɚɛɨɬɵɢɯɚɧɚɥɢɡɢɨɛɫɭɠɞɟɧɢɟ.ȼ Ɋɚɡɞɟɥɟ ɨɩɢɫɚɧ ɫɢɧɬɟɡ ɢɡɭɱɚɟɦɵɯ ɩɨɥɢɦɟɪɧɵɯ ɤɨɦɩɥɟɤɫɨɜɧɢɤɟɥɹ ɫ ɨɫɧɨɜɚɧɢɹɦɢ ɒɢɮɮɚ, ɩɪɢɜɟɞɟɧɵ ɢɯ ɫɬɪɭɤɬɭɪɵ Ɋɢɫ ) ɢɨɛɨɫɧɨɜɚɧ ɜɵɛɨɪ ɢɦɟɧɧɨ ɷɬɢɯ ɤɨɦɩɥɟɤɫɨɜ ɞɥɹ ɢɡɭɱɟɧɢɹ ɜ ɞɚɧɧɨɣɪɚɛɨɬɟ ɩɨ ɩɪɢɱɢɧɟ ɪɚɡɥɢɱɧɵɯ ɷɥɟɤɬɪɨɧɧɵɯ ɢ ɫɬɟɪɢɱɟɫɤɢɯ ɷɮɮɟɤɬɨɜɡɚɦɟɫɬɢɬɟɥɟɣ.Ɋɢɫ1 – ɋɬɪɭɤɬɭɪɵɢɡɭɱɚɟɦɵɯɩɨɥɢɦɟɪɨɜɫɨɛɳɟɣɮɨɪɦɭɥɨɣSRO\>1L6ɫKLII@Ⱦɚɥɟɟ ɞɥɹ ɭɩɪɨɳɟɧɢɹ ɢɡɥɨɠɟɧɢɹ ɩɨɥɢɦɟɪɧɵɟ ɤɨɦɩɥɟɤɫɵ ɥɢɝɚɧɞɵɤɨɬɨɪɵɯɫɨɞɟɪɠɚɬɦɟɬɨɤɫɢɡɚɦɟɫɬɢɬɟɥɶɜɨɪɬɨ-ɩɨɥɨɠɟɧɢɢɮɟɧɢɥɶɧɨɝɨ7ɤɨɥɶɰɚpoly[NiɋH3ɈSalen)],poly[NiɋH3ɈSalphen@ɢpoly[NiɋH3ɈSaltmen@ ɛɭɞɭɬ ɧɚɡɵɜɚɬɶɫɹ ɦɟɬɨɤɫɢɥɢɪɨɜɚɧɧɵɦɢ ɚ ɧɟɫɨɞɟɪɠɚɳɢɟɟɝɨpoly[Ni(Salen)], poly[Ni(Salphen@ɢpoly[Ni(Saltmen)])– ɧɟɦɟɬɨɤɫɢɥɢɪɨɜɚɧɧɵɦɢɊɚɡɞɟɥ 3.2 ɩɨɫɜɹɳɟɧ ɢɡɭɱɟɧɢɸ ɫɬɪɭɤɬɭɪɧɨ-ɮɢɡɢɱɟɫɤɢɯ ɫɜɨɣɫɬɜɢɡɭɱɚɟɦɵɯ ɤɨɦɩɥɟɤɫɨɜ Ȼɵɥɨ ɨɩɪɟɞɟɥɟɧɨ ɱɬɨ ɦɨɪɮɨɥɨɝɢɹ ɜɫɟɯɢɡɭɱɚɟɦɵɯ ɩɥɟɧɨɤ ɡɚɜɢɫɢɬ ɜ ɨɫɧɨɜɧɨɦ ɨɬ ɫɬɪɭɤɬɭɪɵ ɞɢɚɦɢɧɨɜɨɝɨɦɨɫɬɚ ɚ ɢɯ ɩɥɨɬɧɨɫɬɶ ɨɩɪɟɞɟɥɹɟɬɫɹ ɤɚɤ ɫɬɪɭɤɬɭɪɨɣ ɦɨɫɬɚ ɬɚɤ ɢɡɚɦɟɫɬɢɬɟɥɹɦɢ ɜ ɮɟɧɢɥɶɧɵɯ ɤɨɥɶɰɚɯ ɥɢɝɚɧɞɚ ȼ ɞɚɥɶɧɟɣɲɟɦɩɨɥɭɱɟɧɧɵɟ ɩɥɨɬɧɨɫɬɢ ɩɥɟɧɨɤ ɛɵɥɢ ɢɫɩɨɥɶɡɨɜɚɧɵ ɞɥɹ ɪɚɫɱɺɬɨɜ ɢɯɬɨɥɳɢɧɵȼ Ɋɚɡɞɟɥɟ 3.3 ɩɪɟɞɫɬɚɜɥɟɧɵ ɜɨɥɶɬɚɦɩɟɪɨɝɪɚɦɦɵ ɷɥɟɤɬɪɨɞɨɜɦɨɞɢɮɢɰɢɪɨɜɚɧɧɵɯ ɩɥɟɧɤɚɦɢ ɤɨɦɩɥɟɤɫɨɜ ɫɚɥɟɧɨɜɨɝɨ ɬɢɩɚ ɞɥɹɤɨɬɨɪɵɯ ɯɚɪɚɤɬɟɪɧɨ ɧɚɥɢɱɢɟ ɩɥɟɱ ɢɢɥɢ ɞɜɭɯ ɩɚɪ ɩɢɤɨɜ (Ɋɢɫ ).Ɉɩɪɟɞɟɥɟɧɨ ɱɬɨ ɡɚɜɢɫɢɦɨɫɬɶ ɬɨɤɨɜ ɩɢɤɨɜ ɨɬ ɫɤɨɪɨɫɬɟɣ ɪɚɡɜɺɪɬɤɢɛɥɢɡɤɚ ɤ ɥɢɧɟɣɧɨɣ ɤɚɤ ɞɥɹ ɦɟɬɨɤɫɢɥɢɪɨɜɚɧɧɵɯ ɬɚɤ ɢ ɞɥɹɧɟɦɟɬɨɤɫɢɥɢɪɨɜɚɧɧɵɯɤɨɦɩɥɟɤɫɨɜ.ɚ0.15poly[Ni(Salen)]poly[Ni(Salphen)]poly[Ni(Satmen)]0.100.150.100.05,ɦ$,ɦ$0.050.00-0.050.00-0.05-0.10-0.10-0.15ɛpoly[Ni(CH3OSalen)]poly[Ni(CH3OSalphen)]poly[Ni(CH3OSatmen)]-0.15-0.4-0.20.00.20.40.6-0.4E, B-0.20.00.20.40.6(ȼɊɢɫ 2 - ɐɢɤɥɢɱɟɫɤɢɟ ɜɨɥɶɬɚɦɩɟɪɨɝɪɚɦɦɵ ɩɨɥɢɦɟɪɧɵɯ ɤɨɦɩɥɟɤɫɨɜSRO\>1L6FKLII@ ɫɤɨɪɨɫɬɶ ɪɚɡɜɟɪɬɤɢ ɦȼɫ ɮɨɧɨɜɵɣ ɷɥɟɤɬɪɨɥɢɬ Ɏɗ) (0,1 ɫɦ2 ɚɆ ɋ2H5)4NBF4 Ⱥɇ ɩɥɨɳɚɞɶ ɪɚɛɨɱɟɝɨ ɷɥɟɤɬɪɨɞɚɧɟɦɟɬɨɤɫɢɥɢɪɨɜɚɧɧɵɯɤɨɦɩɥɟɤɫɨɜɛɦɟɬɨɤɫɢɥɢɪɨɜɚɧɧɵɯɤɨɦɩɥɟɤɫɨɜȼɨɡɧɢɤɧɨɜɟɧɢɟ ɬɚɤɢɯ ɨɫɨɛɟɧɧɨɫɬɟɣ ɜɨɥɶɬɚɦɩɟɪɧɵɯ ɤɪɢɜɵɯɨɛɴɹɫɧɹɟɬɫɹɩɪɨɬɟɤɚɧɢɟɦɩɨɦɟɧɶɲɟɣɦɟɪɟɞɜɭɯɩɪɨɰɟɫɫɨɜɩɟɪɟɧɨɫɚɡɚɪɹɞɚ ɬɟ ɫɭɳɟɫɬɜɨɜɚɧɢɟɦ ɤɚɤ ɦɢɧɢɦɭɦ ɞɜɭɯ ɨɤɢɫɥɟɧɧɵɯ ɮɨɪɦɮɪɚɝɦɟɧɬɨɜ ɩɥɟɧɨɤ Ɉɞɧɚɤɨ ɱɢɫɥɨ ɷɥɟɤɬɪɨɧɨɜ ɤɨɬɨɪɨɟ ɬɪɚɬɢɬɫɹ ɩɪɢɨɤɢɫɥɟɧɢɢɜɨɫɫɬɚɧɨɜɥɟɧɢɢɩɨɥɢɦɟɪɨɜɛɥɢɡɤɨɤɟɞɢɧɢɰɟɢɡɪɚɫɱɺɬɚɧɚɨɞɢɧɦɨɧɨɦɟɪɧɵɣɮɪɚɝɦɟɧɬȼɉɨɞɪɚɡɞɟɥɟ ɩɪɢɜɟɞɟɧɵɨɫɧɨɜɧɵɟɜɵɜɨɞɵɪɚɡɞɟɥɚɊɚɡɞɟɥ 3.4 ɩɨɫɜɹɳɟɧ ɢɡɭɱɟɧɢɸ ɩɨɥɢɦɟɪɧɵɯ ɤɨɦɩɥɟɤɫɨɜ ɧɢɤɟɥɹ ɫɨɫɧɨɜɚɧɢɹɦɢ ɒɢɮɮɚ ɦɟɬɨɞɨɦ ɗɄȽɆ ɍɫɬɚɧɨɜɥɟɧɨ ɱɬɨ ɧɚ8ɡɚɜɢɫɢɦɨɫɬɹɯɦɚɫɫɵǻm ɨɬɡɚɪɹɞɚɨɤɢɫɥɟɧɢɹ-ɜɨɫɫɬɚɧɨɜɥɟɧɢɹ Qredox ɤɚɤɞɥɹ ɦɟɬɨɤɫɢɥɢɪɨɜɚɧɧɵɯ Ɋɢɫ ɛ ɬɚɤ ɢ ɧɟɦɟɬɨɤɫɢɥɢɪɨɜɚɧɧɵɯɤɨɦɩɥɟɤɫɨɜɊɢɫ ɚɧɚɛɥɸɞɚɸɬɫɹɞɜɚɥɢɧɟɣɧɵɯɭɱɚɫɬɤɚɛɚ2.01.5'm, Pɝɫɦ2'm, Pɝɫɦ21.51.00.51.00.5E ȼE ȼ0.00.001QredoxɦɄɥɫɦ2021QredoxɦɄɥɫɦ22Ɋɢɫ3 - Ɂɚɜɢɫɢɦɨɫɬɶɢɡɦɟɧɟɧɢɹɦɚɫɫɵɨɬɢɡɦɟɧɟɧɢɹɡɚɪɹɞɚɩɪɢɪɟɝɢɫɬɪɚɰɢɢɜɨɥɶɬɚɦɩɟɪɧɵɯ ɤɪɢɜɵɯ ɩɨɥɢɦɟɪɧɵɯ ɤɨɦɩɥɟɤɫɨɜ ɚ) poly[Ni(Saltmen@ ɛ)poly[Ni(CH3OSaltmen)]ȼɟɪɨɹɬɧɨ, ɧɚɥɢɱɢɟ ɬɚɤɢɯ ɭɱɚɫɬɤɨɜ ɫɜɢɞɟɬɟɥɶɫɬɜɭɟɬ ɨ ɬɨɦ ɱɬɨɨɤɢɫɥɟɧɢɟ ɩɨɥɢɦɟɪɧɵɯ ɤɨɦɩɥɟɤɫɨɜ ɧɢɤɟɥɹ ɫ ɨɫɧɨɜɚɧɢɹɦɢ ɒɢɮɮɚɩɪɨɢɫɯɨɞɢɬ ɜ ɞɜɟ ɫɬɚɞɢɢ ɇɚ ɩɟɪɜɨɣ ɫɬɚɞɢɢ ɩɪɨɰɟɫɫɚ ɡɚɪɹɠɟɧɢɹɤɨɬɨɪɚɹɡɚɤɚɧɱɢɜɚɟɬɫɹɩɪɢɩɨɬɟɧɰɢɚɥɚɯɷɥɟɤɬɪɨɞɚ ÷ ȼɩɨɬɨɤɡɚɪɹɞ-ɤɨɦɩɟɧɫɢɪɭɸɳɢɯɚɧɢɨɧɨɜɩɪɨɬɢɜɨɩɨɥɨɠɟɧɩɨɬɨɤɭɪɚɫɬɜɨɪɢɬɟɥɹ Ɂɚɪɹɞ ɤɨɬɨɪɵɣ ɡɚɬɪɚɱɢɜɚɟɬɫɹ ɧɚ ɷɬɨɣ ɫɬɚɞɢɢ ɧɟɡɚɜɢɫɢɬɨɬɫɬɪɭɤɬɭɪɵɥɢɝɚɧɞɚ.

ɇɚɜɬɨɪɨɣɫɬɚɞɢɢɩɪɢɩɨɬɟɧɰɢɚɥɚɯɨɬ0,4 ÷ ȼ ɞɨ ȼ ɩɨɬɨɤɢ ɚɧɢɨɧɨɜ ɢ ɪɚɫɬɜɨɪɢɬɟɥɹ ɢɞɭɬ ɜ ɨɞɧɨɦɧɚɩɪɚɜɥɟɧɢɢ ɢ ɡɚɪɹɞ ɤɨɬɨɪɵɣ ɡɚɬɪɚɱɢɜɚɟɬɫɹ ɜ ɩɪɨɰɟɫɫɟ ɨɤɢɫɥɟɧɢɹɜɨɫɫɬɚɧɨɜɥɟɧɢɹ ɡɚɜɢɫɢɬ ɨɬ ɫɬɪɭɤɬɭɪɵ ɥɢɝɚɧɞɚ. ɋɥɟɞɨɜɚɬɟɥɶɧɨ, ɩɪɢɩɪɨɬɟɤɚɧɢɢ ɪɟɞɨɤɫ-ɩɪɨɰɟɫɫɨɜ ɨɛɪɚɡɭɟɬɫɹ ɞɜɟ ɨɤɢɫɥɟɧɧɵɟ ɮɨɪɦɵɩɨɥɢɦɟɪɚ ɩɨ-ɪɚɡɧɨɦɭ ɜɡɚɢɦɨɞɟɣɫɬɜɭɸɳɢɟ ɫ ɪɚɫɬɜɨɪɢɬɟɥɟɦ ɢɜɟɪɨɹɬɧɨ ɢɯ ɜɨɡɧɢɤɧɨɜɟɧɢɟ ɢ ɩɟɪɟɯɨɞ ɞɪɭɝ ɜ ɞɪɭɝɚ ɨɬɜɟɬɫɬɜɟɧɧɵ ɡɚɜɨɡɧɢɤɧɨɜɟɧɢɟ ɩɥɟɱ ɢɥɢ ɞɜɭɯ ɩɢɤɨɜ ɧɚ ɐȼȺ-ɤɪɢɜɵɯ ɢɫɫɥɟɞɭɟɦɵɯɩɥɺɧɨɤ ɉɪɢɫɭɬɫɬɜɢɟ ɜ ɩɥɟɧɤɚɯ ɞɜɭɯ ɨɤɢɫɥɟɧɧɵɯ ɮɨɪɦ ɩɪɢɩɪɨɬɟɤɚɧɢɢ ɪɟɞɨɤɫ-ɩɪɨɰɟɫɫɨɜ ɚ ɫɥɟɞɨɜɚɬɟɥɶɧɨ ɞɜɭɯ ɬɢɩɨɜ©ɧɟɩɨɞɜɢɠɧɵɯª ɧɨɫɢɬɟɥɟɣ ɡɚɪɹɞɚ ɛɵɥɨ ɜ ɞɚɥɶɧɟɣɲɟɦ ɧɚɩɪɹɦɭɸɩɨɞɬɜɟɪɠɞɟɧɨ ɦɟɬɨɞɨɦ ɜɨɥɶɬɚɛɫɨɪɛɬɨɦɟɬɪɢɢ ɜ ɪɚɛɨɬɟ ɚɫɩɢɪɚɧɬɤɢɇɨɜɨɠɢɥɨɜɨɣ Ɇȼ ɍɫɬɚɧɨɜɥɟɧɧɨɟ ɧɚɥɢɱɢɟ ɞɜɭɯ ɨɤɢɫɥɟɧɧɵɯ ɮɨɪɦ ɜɩɥɟɧɤɚɯ ɩɪɢɜɟɥɨ ɤ ɪɚɡɜɢɬɢɸ ɫɨɨɬɜɟɬɫɬɜɭɸɳɢɯ ɬɟɨɪɟɬɢɱɟɫɤɢɯɩɪɟɞɫɬɚɜɥɟɧɢɣɄɪɨɦɟ ɬɨɝɨ ɜ ɪɚɛɨɬɟ ɛɵɥɚ ɪɚɡɪɚɛɨɬɚɧɚ ɤɨɧɤɪɟɬɧɚɹ ɩɪɨɰɟɞɭɪɚɨɩɪɟɞɟɥɟɧɢɹɬɨɥɳɢɧɵɩɨɥɢɦɟɪɧɵɯɤɨɦɩɥɟɤɫɨɜɧɢɤɟɥɹɫɨɫɧɨɜɚɧɢɹɦɢɒɢɮɮɚ ɫ ɢɫɩɨɥɶɡɨɜɚɧɢɟɦ ɞɚɧɧɵɯ ɗɄȽɆ ɉɨ ɩɨɥɭɱɟɧɧɵɦ9=Ɉɦɫɦ2ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɦ ɞɚɧɧɵɦ ɨɩɪɟɞɟɥɹɥɨɫɶ ɢɡɦɟɧɟɧɢɟ ɪɟɡɨɧɚɧɫɧɨɣɱɚɫɬɨɬɵ ɤɨɥɟɛɚɧɢɣ ɤɜɚɪɰɟɜɨɝɨ ɤɪɢɫɬɚɥɥɚ ɩɪɢ ɩɨɥɢɦɟɪɢɡɚɰɢɢ ɧɚ ɧɺɦɩɥɟɧɨɤ ɫɚɥɟɧɨɜɵɯ ɤɨɦɩɥɟɤɫɨɜ ɡɚɬɟɦ ɦɚɫɫɚ ɫɭɯɢɯ ɩɥɟɧɨɤ mɗɄȽɆɪɚɫɫɱɢɬɵɜɚɥɚɫɶ ɩɨ ɭɪɚɜɧɟɧɢɸ Ɂɚɭɟɪɛɪɟɹ.

Ⱦɥɹ ɫɪɚɜɧɟɧɢɹ ɦɚɫɫɵɩɥɟɧɨɤmɪɚɫɱɺɬ ɛɵɥɢɪɚɫɫɱɢɬɚɧɵɩɨɭɪɚɜɧɟɧɢɸɎɚɪɚɞɟɹ ɉɨɤɚɡɚɧɨɱɬɨɦɚɫɫɵ ɩɨɥɢɦɟɪɧɵɯ ɩɥɟɧɨɤ ɫɚɥɟɧɨɜɵɯ ɤɨɦɩɥɟɤɫɨɜ ɨɩɪɟɞɟɥɟɧɧɵɟ ɢɡɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɯɞɚɧɧɵɯɫɨɜɩɚɞɚɸɬɫɜɟɥɢɱɢɧɚɦɢɜɵɱɢɫɥɟɧɧɵɦɢɩɨ ɡɚɤɨɧɭ Ɏɚɪɚɞɟɹ Ɍɚɤɢɦ ɨɛɪɚɡɨɦ ɬɨɥɳɢɧɚ ɩɨɥɢɦɟɪɧɵɯ ɩɥɟɧɨɤɦɨɠɟɬɛɵɬɶɪɚɫɫɱɢɬɚɧɚɩɪɢɢɡɜɟɫɬɧɨɣɩɥɨɬɧɨɫɬɢɢɡɚɪɹɞɟɫɢɧɬɟɡɚ.ȼ Ɋɚɡɞɟɥɟ ɩɪɨɜɟɞɟɧɨ ɨɩɪɟɞɟɥɟɧɢɟ ɩɚɪɚɦɟɬɪɨɜ ɩɟɪɟɧɨɫɚ ɡɚɪɹɞɚ ɜɩɥɟɧɤɚɯɩɨɥɢɦɟɪɧɵɯɤɨɦɩɥɟɤɫɚɯɫɚɥɟɧɨɜɨɝɨɬɢɩɚɩɨɞɚɧɧɵɦ Ɏɂ ɇɚɊɢɫ 4 ɩɪɟɞɫɬɚɜɥɟɧɚ ɞɢɚɝɪɚɦɦɚ ɇɚɣɤɜɢɫɬɚ ɞɥɹ ɩɨɥɢɦɟɪɧɨɣ ɩɥɟɧɤɢɤɨɦɩɥɟɤɫɚpoly[Ni(Salen)].Ʉɚɤ ɜɢɞɧɨ ɢɡ ɩɪɟɞɫɬɚɜɥɟɧɧɨɝɨ100050ɪɢɫɭɧɤɚ ɧɚ ɝɨɞɨɝɪɚɮɚɯ ɜɫɟɯ40800ɢɡɭɱɚɟɦɵɯɤɨɦɩɥɟɤɫɨɜ30-0,2V 20ɨɬɫɭɬɫɬɜɭɸɬɯɚɪɚɤɬɟɪɧɵɟ600-0,1V100Vɭɱɚɫɬɤɢɫɨɨɬɜɟɬɫɬɜɭɸɳɢɟ0,1V 04000 10 20 30 40 500,2Vɫɬɚɧɞɚɪɬɧɵɦɷɥɟɦɟɧɬɚɦ0,3V2000,4Vɷɤɜɢɜɚɥɟɧɬɧɵɯ ɫɯɟɦ ɤɨɬɨɪɵɟ0,5V0,6V0ɨɛɵɱɧɨ ɢɫɩɨɥɶɡɭɸɬɫɹ ɩɪɢ02004006008001000ɨɛɪɚɛɨɬɤɟ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɯZ', Ɉɦɫɦ2Ɋɢɫ 4 - Ⱦɢɚɝɪɚɦɦɵ ɇɚɣɤɜɢɫɬɚ ɞɚɧɧɵɯɎɂ. Ɍɚɤɨɣɫɦɟɲɚɧɧɵɣɡɚɪɟɝɢɫɬɪɢɪɨɜɚɧɧɵɟ ɩɪɢ ɪɚɡɥɢɱɧɵɯ ɯɚɪɚɤɬɟɪ ɡɚɜɢɫɢɦɨɫɬɢ Z(Ȧ),ɨɩɨɪɧɵɯ ɩɨɬɟɧɰɢɚɥɚɯ ɞɥɹ ɩɨɥɢɦɟɪɧɵɯ ɫɜɹɡɚɧɧɵɣ ɩɨ-ɜɢɞɢɦɨɦɭ ɫɤɨɦɩɥɟɤɫɚpoly[Ni(Salen)].ɧɚɥɢɱɢɟɦ ɩɨ ɦɟɧɶɲɟɣ ɦɟɪɟɞɜɭɯɨɤɢɫɥɟɧɧɵɯɮɨɪɦɩɨɥɢɦɟɪɧɵɯ ɤɨɦɩɥɟɤɫɨɜ ɧɚɛɥɸɞɚɟɬɫɹ ɢ ɜ ɫɥɭɱɚɟ ɩɥɟɧɨɤ ɞɪɭɝɢɯɧɟɦɟɬɨɤɫɢɥɢɪɨɜɚɧɧɵɯ ɢ ɦɟɬɨɤɫɢɥɢɪɨɜɚɧɧɵɯ ɤɨɦɩɥɟɤɫɨɜ ɉɨɷɬɨɦɭɞɥɹ ɨɩɪɟɞɟɥɟɧɢɹ ɩɚɪɚɦɟɬɪɨɜ ɩɟɪɟɧɨɫɚ ɡɚɪɹɞɚ ɜ ɩɨɥɢɦɟɪɧɵɯ ɩɥɟɧɤɚɯɤɨɦɩɥɟɤɫɨɜ poly[Ni(Schiff)] - ɷɮɮɟɤɬɢɜɧɨɝɨ ɤɨɷɮɮɢɰɢɟɧɬɚ ɞɢɮɮɭɡɢɢ‫ܦ‬௘௙ ɤɨɬɨɪɵɣ ɯɚɪɚɤɬɟɪɢɡɭɟɬ ɫɭɦɦɚɪɧɭɸ ɞɢɮɮɭɡɢɸ ɷɥɟɤɬɪɨɧɨɜ ɢɩɪɨɬɢɜɨɢɨɧɨɜɢɺɦɤɨɫɬɢɩɪɢɧɢɡɤɢɯɱɚɫɬɨɬɚɯCLF ɬɨɟɫɬɶ©ɩɨɥɟɡɧɨɣªɺɦɤɨɫɬɢ ɷɧɟɪɝɨɡɚɩɚɫɚɸɳɢɯ ɭɫɬɪɨɣɫɬɜ ɛɵɥ ɢɫɩɨɥɶɡɨɜɚɧ ɦɨɞɟɥɶɧɵɣɩɨɞɯɨɞ.

ɉɪɢ ɬɚɤɨɦ ɩɨɞɯɨɞɟ ɞɥɹ ɨɩɪɟɞɟɥɟɧɢɹ ɤɨɥɢɱɟɫɬɜɟɧɧɵɯɡɧɚɱɟɧɢɣ ɩɚɪɚɦɟɬɪɨɜ ɩɟɪɟɧɨɫɚ ɢɫɩɨɥɶɡɭɟɬɫɹ ɩɨɥɧɨɟ ɦɚɬɟɦɚɬɢɱɟɫɤɨɟɭɪɚɜɧɟɧɢɟ ɞɥɹ ɢɦɩɟɞɚɧɫɚ ɩɨɥɭɱɟɧɧɨɟ ɜ ɪɟɡɭɥɶɬɚɬɟ ɞɟɬɚɥɶɧɨɝɨɚɧɚɥɢɡɚɜɫɟɯɜɨɡɦɨɠɧɵɯɮɢɡɢɤɨ-ɯɢɦɢɱɟɫɤɢɯɩɪɨɰɟɫɫɨɜɩɪɨɢɫɯɨɞɹɳɢɯ ɜ ɦɨɞɢɮɢɰɢɪɨɜɚɧɧɨɦ ɷɥɟɤɬɪɨɞɟ ȼ ɪɚɛɨɬɟ10ɢɫɩɨɥɶɡɨɜɚɥɨɫɶ ɞɜɚ ɦɟɬɨɞɚ: ©ɤɥɚɫɫɢɱɟɫɤɢɣª ɦɟɬɨɞ Ɇɚɬɢɚɫɚ-ɏɚɚɫɚ,ɤɨɬɨɪɵɣɪɚɡɪɚɛɨɬɚɧɞɥɹɫɢɫɬɟɦɜɤɨɬɨɪɵɯɩɪɢɫɭɬɫɬɜɭɟɬɬɨɥɶɤɨɨɞɢɧɧɟɩɨɞɜɢɠɧɵɣ ɧɨɫɢɬɟɥɶ ɡɚɪɹɞɚ ɢ ɧɨɜɵɣ (©ɪɟɞɭɰɢɪɨɜɚɧɧɵɣª) ɦɟɬɨɞ.ɗɬɨɬ ɦɟɬɨɞ ɭɱɢɬɵɜɚɟɬ ɧɚɥɢɱɢɟ ɞɜɭɯ ɧɟɩɨɞɜɢɠɧɵɯ ɧɨɫɢɬɟɥɟɣ ɬɨɤɚ ɜɩɥɟɧɤɚɯɫɚɥɟɧɨɜɵɯɤɨɦɩɥɟɤɫɨɜ.ɉɪɢɢɫɩɨɥɶɡɨɜɚɧɢɢ©ɪɟɞɭɰɢɪɨɜɚɧɧɨɝɨª ɦɟɬɨɞɚ ɞɥɹ ɨɩɪɟɞɟɥɟɧɢɹ ɩɚɪɚɦɟɬɪɨɜ ɩɟɪɟɧɨɫɚɬɪɟɛɭɟɬɫɹ ɩɨɫɬɪɨɢɬɶ ɡɚɜɢɫɢɦɨɫɬɶ -=¶¶Ȧ1/2 = fȦ-1/2) ɤɨɬɨɪɚɹɨɤɚɡɵɜɚɟɬɫɹɥɢɧɟɣɧɨɣɂɡɩɨɥɭɱɟɧɧɨɣɡɚɜɢɫɢɦɨɫɬɢɦɨɠɧɨɨɩɪɟɞɟɥɢɬɶɧɢɡɤɨɱɚɫɬɨɬɧɭɸ ɺɦɤɨɫɬɶ CLF ɤɚɤ ɬɚɧɝɟɧɫ ɭɝɥɚ ɧɚɤɥɨɧɚ ɥɢɧɟɣɧɨɝɨɭɱɚɫɬɤɚɤɪɢɜɨɣGí=Ȧ1/2GȦí1/2ɉɨɬɨɦɭɠɟɝɪɚɮɢɤɭɨɩɪɟɞɟɥɹɟɬɫɹɤɨɧɫɬɚɧɬɚ ȼɚɪɛɭɪɝɚ ߪௐ ɤɚɤ ɡɧɚɱɟɧɢɟ ɨɬɫɟɤɚɟɦɨɟ ɧɚ ɨɫɢ íZ''·Ȧ1/2ɩɪɹɦɨɣ ɷɤɫɬɪɚɩɨɥɢɪɭɸɳɟɣ ɬɚɤɨɣ ɥɢɧɟɣɧɵɣ ɭɱɚɫɬɨɤ ɂɫɩɨɥɶɡɨɜɚɧɢɟ©ɪɟɞɭɰɢɪɨɜɚɧɧɨɝɨª ɦɟɬɨɞɚ ɩɨɡɜɨɥɹɟɬ ɡɧɚɱɢɬɟɥɶɧɨ ɫɧɢɡɢɬɶ ɤɚɤ ɜɪɟɦɹɨɛɪɚɛɨɬɤɢ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɯ ɞɚɧɧɵɯ Ɏɂ ɬɚɤ ɢ ɨɲɢɛɤɭ ɪɚɫɱɺɬɚɩɚɪɚɦɟɬɪɨɜ ɩɟɪɟɧɨɫɚ ɇɚ Ɋɢɫ 5 ɩɪɟɞɫɬɚɜɥɟɧɵ ɡɚɜɢɫɢɦɨɫɬɢɩɚɪɚɦɟɬɪɨɜ ɩɟɪɟɧɨɫɚ ɡɚɪɹɞɚ ɢɡɭɱɚɟɦɵɯ ɤɨɦɩɥɟɤɫɨɜ ɨɬ ɩɨɬɟɧɰɢɚɥɚɪɚɫɫɱɢɬɚɧɧɵɟɫɩɨɦɨɳɶɸɨɛɨɢɯɦɟɬɨɞɨɜɚ0.0301E-70.020Defɫɦ2ɫCLFɎɫɦ20.0250.0150.0100.0051E-81E-91E-100.000-0.20.00.20.40.60.00.2(ȼɛ0.0300.40.61E-60.0251E-70.020Defɫɦ2ɫCLFɎɫɦ2(ȼ0.0150.0100.0051E-81E-91E-100.000-0.20.00.20.40.6-0.20.00.20.40.6(ȼ(ȼɊɢɫ 5 - ɉɚɪɚɦɟɬɪɵ ɩɟɪɟɧɨɫɚ ɚ ɧɢɡɤɨɱɚɫɬɨɬɧɚɹ ɟɦɤɨɫɬɶ ɢ ɷɮɮɟɤɬɢɜɧɵɣɤɨɷɮɮɢɰɢɟɧɬ ɞɢɮɮɭɡɢɢ ɞɥɹ ɩɥɟɧɨɤ ɧɟɦɟɬɨɤɫɢɥɢɪɨɜɚɧɧɵɯ ɤɨɦɩɥɟɤɫɨɜpoly[Ni(Salen)], poly[Ni(SalpKHQ@ ɢ SRO\>1L6DOWPHQ@ ɛ ɧɢɡɤɨɱɚɫɬɨɬɧɚɹɟɦɤɨɫɬɶ ɢ ɷɮɮɟɤɬɢɜɧɵɣ ɤɨɷɮɮɢɰɢɟɧɬ ɞɢɮɮɭɡɢɢ ɞɥɹ ɩɥɟɧɨɤ11ɦɟɬɨɤɫɢɥɢɪɨɜɚɧɧɵɯɤɨɦɩɥɟɤɫɨɜSRO\>1LCH3OSalen)], poly[Ni(CH3OSalphen)]ɢSRO\>1LCH3OSaltmen)].Ⱥɧɚɥɢɡ ɩɚɪɚɦɟɬɪɨɜ ɩɟɪɟɧɨɫɚ ɡɚɪɹɞɚ ɜ ɩɨɥɢɦɟɪɧɵɯ ɩɥɺɧɤɚɯɤɨɦɩɥɟɤɫɨɜ ɧɢɤɟɥɹ ɫ ɨɫɧɨɜɚɧɢɹɦɢ ɒɢɮɮɚ ɪɚɡɥɢɱɧɨɣ ɫɬɪɭɤɬɭɪɵɩɨɤɚɡɚɥ ɱɬɨ ɜɜɟɞɟɧɢɟ ɡɚɦɟɫɬɢɬɟɥɟɣ ɜ ɫɬɪɭɤɬɭɪɭ ɥɢɝɚɧɞɚ ɩɪɢɜɨɞɢɬ ɤɭɜɟɥɢɱɟɧɢɸ ɷɮɮɟɤɬɢɜɧɨɝɨ ɤɨɷɮɮɢɰɢɟɧɬɚ ɞɢɮɮɭɡɢɢ ɜ ɩɨɥɢɦɟɪɧɵɯɦɚɬɟɪɢɚɥɚɯ ɉɪɢ ɷɬɨɦ ɡɚɤɨɧɨɦɟɪɧɨɫɬɢ ɜɥɢɹɧɢɹ ɡɚɦɟɫɬɢɬɟɥɟɣ ɧɚɺɦɤɨɫɬɶ ɦɚɬɟɪɢɚɥɨɜ ɞɨɫɬɚɬɨɱɧɨ ɫɥɨɠɧɵ ɢ ɩɨɤɚ ɧɟ ɩɨɞɞɚɸɬɫɹɨɞɧɨɡɧɚɱɧɨɦɭ ɬɨɥɤɨɜɚɧɢɸ.

Ɇɢɧɢɦɚɥɶɧɵɟ ɡɧɚɱɟɧɢɹ ɺɦɤɨɫɬɢɞɟɦɨɧɫɬɪɢɪɭɸɬɤɨɦɩɥɟɤɫɵSRO\>1L6DOpKHQ@ɢSRO\>1L&+3OSaltmen)],ɺɦɤɨɫɬɢɨɫɬɚɥɶɧɵɯɦɚɬɟɪɢɚɥɨɜɛɥɢɡɤɢɞɪɭɝɤɞɪɭɝɭɊɚɡɞɟɥ ɫɨɞɟɪɠɚɳɢɣ ɬɪɢ ɩɨɞɪɚɡɞɟɥɚ ɩɨɫɜɹɳɟɧ ɢɡɭɱɟɧɢɸɫɬɚɛɢɥɶɧɨɫɬɢ ɩɨɥɢɦɟɪɧɵɯɤɨɦɩɥɟɤɫɨɜɧɢɤɟɥɹɫɨɫɧɨɜɚɧɢɹɦɢɒɢɮɮɚɜɩɪɢɫɭɬɫɬɜɢɢɨɫɧɨɜɚɧɢɣɅɶɸɢɫɚɜɪɚɫɬɜɨɪɟɮɨɧɨɜɨɝɨɷɥɟɤɬɪɨɥɢɬɚȼ ɉɨɞɪɚɡɞɟɥɟ ɢɡɥɨɠɟɧɵ ɞɚɧɧɵɟ ɩɨ ɫɬɚɛɢɥɶɧɨɫɬɢ ɩɥɟɧɨɤɫɚɥɟɧɨɜɵɯ ɤɨɦɩɥɟɤɫɨɜ ɜ ɪɚɡɧɵɯ ɞɢɚɩɚɡɨɧɚɯ ɪɟɝɢɫɬɪɚɰɢɢɜɨɥɶɬɚɦɩɟɪɧɵɯ ɤɪɢɜɵɯ ɜ ɩɪɢɫɭɬɫɬɜɢɢ ɜɨɞɵ ɜ Ɏɗ Ɋɟɡɭɥɶɬɚɬɵɚɧɚɥɢɡɚɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɯ ɞɚɧɧɵɯ ɩɪɟɞɫɬɚɜɥɟɧɵɧɚ Ɋɢɫ6.Ʉɚɤ ɜɢɞɧɨ ɢɡ ɪɢɫɭɧɤɚ ɩɪɢɚɧɨɞɧɨɦ ɩɪɟɞɟɥɟ ɰɢɤɥɢɪɨɜɚɧɢɹɦɟɧɟɟ ȼ ɫɤɨɪɨɫɬɶ ɞɟɝɪɚɞɚɰɢɢɩɥɟɧɨɤɧɟɦɟɬɨɤɫɢɥɢɪɨɜɚɧɧɵɯpoly [Ni(Salen)]poly [Ni(Salphen)]ɤɨɦɩɥɟɤɫɨɜɧɢɠɟɱɟɦpoly [Ni(Saltmen)]ɦɟɬɨɤɫɢɥɢɪɨɜɚɧɧɵɯ Ɉɞɧɚɤɨ ɩɪɢpoly[Ni(CH 26DOɟQ@ɩɨɜɵɲɟɧɢɢɷɬɨɝɨɩɪɟɞɟɥɚɞɨ0,6 ȼpoly[Ni(CH 26DOɟQ@poly[Ni(CH 26DOɟQ@ɩɥɟɧɤɢɧɟɦɟɬɨɤɫɢɥɢɪɨɜɚɧɧɵɯɩɨɥɢɦɟɪɨɜɧɚɱɢɧɚɟɬȺɧɨɞɧɵɣɩɪɟɞɟɥɰɢɤɥɢɪɨɜɚɧɢɹȼɞɟɝɪɚɞɢɪɨɜɚɬɶɡɧɚɱɢɬɟɥɶɧɨɛɵɫɬɪɟɟ, ɜ ɬɨ ɜɪɟɦɹ ɤɚɤ ɩɥɟɧɤɢɊɢɫ6ɂɡɦɟɧɟɧɢɟɷɥɟɤɬɪɨɚɤɬɢɜɧɨɫɬɢ ɩɨɥɢɦɟɪɨɜ ɩɪɢ ɞɜɭɯ ɢɡ ɬɪɺɯ ɢɫɫɥɟɞɨɜɚɧɧɵɯɞɥɢɬɟɥɶɧɨɦɰɢɤɥɢɪɨɜɚɧɢɢɜ ɦɟɬɨɤɫɢɥɢɪɨɜɚɧɧɵɯ ɤɨɦɩɥɟɤɫɨɜɢɪɚɡɥɢɱɧɵɯɞɢɚɩɚɡɨɧɚɯ (poly[Ni(CH3OSalen)]poly[Ni(CH3OSaltmen)])ɩɨɬɟɧɰɢɚɥɨɜɞɟɦɨɧɫɬɪɢɪɭɸɬ ɧɟɡɧɚɱɢɬɟɥɶɧɨɟɭɜɟɥɢɱɟɧɢɟ ɫɤɨɪɨɫɬɢ ɞɟɝɪɚɞɚɰɢɢ.Ⱥɧɨɦɚɥɶɧɨɟ ɩɨɜɟɞɟɧɢɟ ɩɥɟɧɨɤ ɤɨɦɩɥɟɤɫɚ poly[Ni(CH3OSalphen)],ɚɧɚɥɨɝɢɱɧɨɟ ɩɨɜɟɞɟɧɢɸ ɧɟɦɟɬɨɤɫɢɥɢɪɨɜɚɧɧɵɯ ɤɨɦɩɥɟɤɫɨɜ ɦɨɠɟɬɛɵɬɶ ɫɜɹɡɚɧɨ ɫ ɜɡɚɢɦɧɨɣ ɤɨɦɩɟɧɫɚɰɢɟɣ ɞɨɧɨɪɧɵɯ ɷɥɟɤɬɪɨɧɧɵɯɷɮɮɟɤɬɨɜ ɦɟɬɨɤɫɢɥɶɧɵɯ ɡɚɦɟɫɬɢɬɟɥɟɣ ɜ ɚɥɶɞɟɝɢɞɧɵɯ ɮɪɚɝɦɟɧɬɚɯɥɢɝɚɧɞɚ ɢ ɚɤɰɟɩɬɨɪɧɨɝɨ ɷɮɮɟɤɬɚ ɮɟɧɢɥɶɧɨɝɨ ɡɚɦɟɫɬɢɬɟɥɹ ɜɉɚɞɟɧɢɟɡɚɪɹɞɚɜɨɫɫɬɚɧɨɜɥɟɧɢɹɧɚɰɢɤɥɟɨɬɩɟɪɜɨɝɨɰɢɤɥɚ1008060403203300.40.60.812ɞɢɚɦɢɧɨɜɨɦ ɦɨɫɬɢɤɟ.

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