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    題名: 四銅酸酯及水楊醛與過渡金屬及二氟化硼錯合物之液晶性質探討
    作者: 池忻芸;Chih, Hsin-Yun
    貢獻者: 化學學系
    關鍵詞: 液晶;盤狀液晶;六角柱相;矩形相;二氟化硼;縮合反應;liquid crystal;columnar;hexagonal phases;rectangular phases;BF2 complexes;condensation reaction
    日期: 2021-07-20
    上傳時間: 2021-12-07 11:13:02 (UTC+8)
    出版者: 國立中央大學
    摘要: 系列一,本研究以 tetraketonates 作為核心合成出化合物 1a-c, 1a-c BF2 及金屬錯合物 1b-M (M = Ni, Cu, Pd)。由實驗結果發現,化合物 1a-c 皆不具有液晶性質,而 1b-BF2 (n = 10, 12) 形成 Colr、1c-BF2 (n = 8, 10, 12) 及 1b-Cu (n = 12) 皆表現出筒狀液晶 Colh。化合物 1c-BF2 (n = 12) 為目前少見含雙 BF2 結構之盤狀室溫液晶,並於 BF2 配位後最大放光波長紅移,且螢光強度增強,化合物 1a-c BF2 之放光於溶液下均為黃色,其中 1c-BF2 (n = 12) max = 572 nm 為此系列放光波長最長之分子。
    系列二,近幾年發光液晶同時結合發光特性和自組裝特性,吸引了眾多商業和學術研究關注。然而市售的染料液晶通常會因為聚集而導致猝滅 (aggregation-caused quenching, ACQ) 效應,使應用性受到限制。相反的聚集誘導放光 (aggregation-induced emission, AIE) 不僅改善了螢光焠滅的問題,還表現出良好的介晶性質; Salicylaldimine 常作為 AIE 材料之官能基,因此本研究合成一系列以 pyridine 為核心,且以 Salicylaldimine 作為連接基之發光液晶,由實驗結果發現,化合物 2a (n = 8, 10, 12) 為雙向液晶 SmA, SmC、2a-BF2 (n = 4-12) 皆表現出層狀液晶相。化合物於 BF2 配位後最大放光波長紅移,由 AIE 效應測試發現,當化合物 2a-BF2 (n = 12) 水含量 80 % 時,其放光強度最強 max = 524 nm,ΦF = 71.42 %。
    ;In the first series, columnar bis(BF2)2 complexes, containing tetraketonates as a central core with two β-diketonates incorporated, 1a-c, 1a-c BF2 and 1b-M (M = Ni, Cu, Pd) were prepared. All compounds were characterized by 1H and 13C NMR spectroscopy, and element analysis. Their mesomorphic and optical behavior was studied by polarizing microscope and differential scanning calorimetry and photofluorescence spectrometer. Their phase structures were confirmed by powder X-ray diffraction. Results showed that the derivatives 1a-c were nonmesogenic, while compounds 1b-BF2 (n = 10, 12), 1c-BF2 (n = 8, 10, 12) and 1b-Cu exhibited enantiotropic columnar mesophases. Compound 1c-BF2 (n = 12) was room temperature Colh liquid crystal. Compound 1b-BF2 (n = 8, 10, 12) formed Colr phase. The PL emissions of complexes 1a-c BF2 (n = 8, 10, 12) possess a pronounced green emission in solution. The PL emission of 1b-BF2 (n = 12) showed a strong dependence on structural moiety incorporated with max = 565 nm.

    In the second series, a new of borondifluoride complexes 2a-BF2 derived from eneamines 2a were reported, and their mesomorphic and optical properties were also investigated. The optical property of the boron complexes was dependent on their molecular structures, The maximum absorption and the maximum luminescent emission of the compound 2a-BF2 were red-shifted compared to the compound 2a. The 2a-BF2 (n = 12) have the property of AIE (%v/v = 80% (THF/H2O)) , max = 524 nm, ΦF = 35.71 %), and it can be a protential material of luminescence in the future.
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