Excited-State Dynamics of a Substituted Fluorene Derivative. The Central Role of Hydrogen Bonding Interactions with the Solvent.
Excited-State Dynamics of a Substituted Fluorene Derivative. The Central Role of Hydrogen Bonding Interactions with the Solvent.
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DOI：
10.1021/acs.jpcb.1c06474
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发表时间：
2021-11-11
影响因子：
3.3
通讯作者：
Blanchard, G. J.
中科院分区：
文献类型：
--
作者：
Capistran, Briana A.;Yuwono, Stephen H.;Moemeni, Mehdi;Maity, Soham;Vahdani, Aria;Borhan, Babak;Jackson, James E.;Piecuch, Piotr;Dantus, Marcos;Blanchard, G. J.
取代芴结构表现出不同寻常的光化学性质。先前报道的取代芴席夫碱FR0-SB在光激发下表现出超光碱行为，ΔpKb为~14。为了理解这种不寻常行为的基础，我们使用时间分辨荧光光谱和量子化学计算检查了FR0- sb的结构前体，醛FR0在质子和非质子溶剂中的电子结构和弛化动力学。计算表明，三个激发态的能量相对接近。光谱数据与这些依赖于溶剂羟基官能团的存在和浓度的电子态的弛豫动力学一致。这些结果强调了溶剂氢键与FR0醛氧在调节分子弛豫动力学中的核心作用。
Substituted fluorene structures have demonstrated unusual photochemical properties. Previous reports on the substituted fluorene Schiff base FR0-SB demonstrated super photobase behavior with a ΔpKb of ~14 upon photoexcitation. In an effort to understand the basis for this unusual behavior, we have examined the electronic structure and relaxation dynamics of the structural precursor of FR0-SB, the aldehyde FR0, in protic and aprotic solvents using time-resolved fluorescence spectroscopy and quantum chemical calculations. The calculations show three excited singlet states in relatively close energetic proximity. The spectroscopic data are consistent with relaxation dynamics from these electronic states that depend on the presence and concentration of solvent hydroxyl functionality. These results underscore the central role of solvent hydrogen bonding to the FR0 aldehyde oxygen in mediating the relaxation dynamics within this molecule.
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影响因子：
15
作者：
HERMANT, RM;BAKKER, NAC;VERHOEVEN, JW
通讯作者：
VERHOEVEN, JW
影响因子：
2.3
作者：
BAGCHI, B;OXTOBY, DW;FLEMING, GR
通讯作者：
FLEMING, GR
影响因子：
4.4
作者：
CASTNER, EW;MARONCELLI, M;FLEMING, GR
通讯作者：
FLEMING, GR
影响因子：
2.8
作者：
GELDOF, PA;RETTSCHNICK, RP;HOYTINK, GJ
通讯作者：
HOYTINK, GJ
影响因子：
2.9
作者：
Hunt, Jonathan Ryan;Dawlaty, Jahan M.
通讯作者：
Dawlaty, Jahan M.