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제117회 대한화학회 학술발표회, 총회 및 기기전시회 안내 Aggregation-induced emission of diarylamino-π-carborane triads: Effects of Charge transfer and π-conjugation

등록일
2016년 2월 25일 14시 29분 14초
접수번호
1970
발표코드
INOR.P-114 이곳을 클릭하시면 발표코드에 대한 설명을 보실 수 있습니다.
발표시간
4월 22일 (금요일) 13:00~14:30
발표형식
포스터
발표분야
무기화학
저자 및
공동저자
김소연, 조양진, 한원식1, 조대원, 손호진, 강상욱2,*
고려대학교 신소재화학과, Korea
1서울여자대학교 화학과, Korea
2고려대학교 소재화학과, Korea
Carborane-based donor-π-acceptor triads (D-π-A-π-D) bearing triarylamine moieties were synthesised. All the monomeric triads showed a blue-green emission in a dilute solution, which was assigned as an intramolecular charge-transfer (CT) emission. The intramolecular CT emission showed large Stokes shifts at a higher solvent polarity. The intramolecular CT emission further shifted to a longer wavelength with the increase in π-conjugation. Interestingly, a strong red emission was observed in highly concentrated solutions or in the solid state, which was assigned as an aggregation-induced emission (AIE). Moreover, the AIE strongly depended on solvent polarity. A large Stokes shift in AIE was attributed to the strong CT character. The changes in dipole moment for the AIE state and monomer emission were evaluated using the Lippert–Mataga relationship. The density functional theory calculations showed that the change in electron distribution between the aryl amino group (highest occupied molecular orbital, HOMO) and carborane moiety (lowest unoccupied molecular orbital, LUMO) indicates the intramolecular CT character, and the emission colour changes were attributed to the HOMO–LUMO energy gap controlled by the π-extension of the phenylene linker. The electrochemical properties such as the oxidation and reduction potentials were consistent with the theoretical calculation results. The emission properties were affected by two main factors: the solvent polarity and solubility.

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