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02월 19일 10시 이후 : 초록수정 불가능, 일정확인 및 검색만 가능
제121회 대한화학회 학술발표회, 총회 및 기기전시회 안내
Synthesis and photochemical properties of bis- substituted
-carborane derivatives with aryl moieties
2018년 2월 7일 13시 53분 21초
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4월 19일 (목요일) 11:00~12:30
, Su-Jin Kwak
, Chul Hoon Kim
, Sang Ook Kang
, Ho-Jin Son
Department of Advanced Materials Chemistry, Korea University, Korea
o-Carborane was used to alter the electronic states of π-conjugated organic aryls, and demonstrated to be an effective electron controlling unit which can tune HOMO and LUMO energies for the electron transfer. Two different types of bis-aryl compounds were chosen to this end; one with di-phenyls and its fused fluorenyl and the other with two isomers of naphthyls, α- and β-forms. It has been found that among the series of aryl compounds the second type naphthyls were more susceptible to the electronic alteration and α-isomer of naphthyl showed the most perturbed electronic state. The ground state structures confirmed by the crystallographic measurements provided a close correlation of structure and electronic property in between photo-responsive aryl groups and o-carborane. HOMO and LUMO energies were estimated and confirmed by cyclic voltammograms and DFT calculations, respectively, and proved the authenticity of the electronic alteration. Excited states were calculated by the TD-DFT calculations and correlated with the corresponding absorption spectra to illustrate the electronic perturbation in a systematic fashion that excited state¬¬s were found to be lowered in regard to the electronic perturbation. Therefore, within bis-aryls-o-carborane series, following decreasing energy order is observed; α-Np, β-Np, Flu, diPh and Ph. Final verification of the lowered energy was made from the measurement of the electron transfer efficiency between the well-studied Iridium based photosensitizer, Ir(ppy)
and two typical bis-aryls-o-carboranes, α-Np and Ph and electron transfer efficiency of α-Np is ten times greater than that of Ph.
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