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  • 03월 02일 17시 이후 : 초록수정 불가능, 일정확인 및 검색만 가능

제109회 대한화학회 학술발표회, 총회 및 기기전시회 안내 Deprotonation-Induced Aromaticity Enhancement in meso-Hexakis(pentafluorophenyl) [26]Hexaphyrin(

2012년 2월 28일 13시 38분 23초
PHYS.P-516 이곳을 클릭하시면 발표코드에 대한 설명을 보실 수 있습니다.
4월 25일 (수요일) 18:00~21:00
저자 및
연세대학교 화학과, Korea

During the last decade, expanded porphyrins bearing more than four pyrrole rings have attracted considerable attention in light of their rich chemistry such as structural versatility, effective coordination platforms to realize various metal complexes, organic nonlinear optical materials, new near-infrared (NIR) and infrared (IR) dyes, and easy accessibility of [4n] and [4n+2] congeners through two-electron oxidation and reduction processes. Throughout the studies on expanded porphyrins, we have consistently observed the correlations between photophysical properties and aromaticity in measurements of the magnetic indices, steady-state absorption and emission spectra, time-resolved excited-state dynamics, and computational calculations including the NICS, HOMA, and AICD. Aromatic expanded porphyrins, regardless of whether they are H?ckel- or M?bius-type, exhibit distinct absorption spectra with well-defined, sharp B- and Q-like bands, strong fluorescence, long-lived excited states, and large TPA (two-photon absorption) cross-section values as compared with anti- or nonaromatic expanded porphyrins. as a part of our continuous efforts to explore novel electronic states of expanded porphyrins, we propose a method for controlling aromaticity of normal [26]hexaphyrin by deprotonaton with tetrabutylammonium fluoride (TBAF). Deprotonated monoanion and dianion of hexakis(pentafluorophenyl) [26]hexaphyrin( display sharp B-like bands, remarkably strong fluorescence, and long-lived singlet and triplet excited-states as an indication of enhanced aromaticty. Structural, spectroscopic, and computational studies have revealed that the deprotonation induces structural deformations, which leads to a change in the main conjugated π-electronic circuit as a cause for the enhanced aromaticity.