个人信息Personal Information
副教授
硕士生导师
性别:女
毕业院校:Regensburg大学
学位:博士
所在单位:化学学院
学科:分析化学
电子邮箱:guohm@dlut.edu.cn
Geometry Relaxation-Induced Large Stokes Shift in Red-Emitting Borondipyrromethenes (BODIPY) and Applications in Fluorescent Thiol Probes
点击次数:
论文类型:期刊论文
发表时间:2012-03-02
发表刊物:JOURNAL OF ORGANIC CHEMISTRY
收录刊物:SCIE、EI、PubMed、Scopus
卷号:77
期号:5
页面范围:2192-2206
ISSN号:0022-3263
摘要:2-Thienyl and 2,6-bisthienyl BODIPY derivatives (BS-SS and BS-DS) were prepared that show intense absorption (epsilon = 65000 M-1 cm(-1) at 507 nm) and a large Stokes shift (96 nm) vs the small Stokes shift of typical BODIPY (<15 nm). Control compounds with a thienyl unit at the 8-position or phenyl substituents at the 2,6-positions were prepared (BS-1 and 9). BS-1 shows absorption/emission in the blue-shifted range and a small Stokes shift (12 nm). Compound 9 shows absorption in the red-shifted range, but the Stokes shift (<30 nm) is much smaller than that for BS-SS and BS-DS. DFT calculations propose the large Stokes shifts of BS-SS and BS-DS are due to the remarkable geometry relaxation upon photoexcitation and its substantial effect on the energy levels of molecular orbitals. For the dyes with small Stokes shifts, much smaller geometry relaxations were found. The fluorophores were used for fluorescent thiol probes, with 2,4-dinitrobenzenesulfonyl (DNBS) as the fluorescence switch. Both fluorescence OFF-ON and unprecedented ON-OFF transduction were observed, which are attributed to the different photoinduced intramolecular electron-transfer (PET) profile. All the photophysics were rationalized by DFT calculations based on the concept of "electronic states" instead of the very often used approximation of "molecular orbitals".
上一条:Transition metal complexes with strong absorption of visible light and long-lived triplet excited states: from molecular design to applications
下一条:Fluorescent coumarin derivatives with large stokes shift, dual emission and solid state luminescent properties: An experimental and theoretical study