Predicting the photoinduced electron transfer thermodynamics in polyfluorinated 1,3,5-triarylpyrazolines based on multiple linear free energy relationships.
Predicting the photoinduced electron transfer thermodynamics in polyfluorinated 1,3,5-triarylpyrazolines based on multiple linear free energy relationships.
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基于多个线性自由能关系，预测多氟1,3,5-三吡唑啉的光诱导的电子转移热力学。
DOI：
10.1039/b821042j
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发表时间：
2009-04-21
影响因子：
3.2
通讯作者：
Fahrni CJ
中科院分区：
文献类型：
--
作者：
Verma M;Chaudhry AF;Fahrni CJ
The photophysical properties of 1,3,5-triarylpyrazolines are strongly influenced by the nature and position of substituents attached to the aryl-rings, rendering this fluorophore platform well suited for the design of fluorescent probes utilizing a photoinduced electron transfer (PET) switching mechanism. To explore the tunability of two key parameters that govern the PET thermodynamics, the excited state energy ΔE00 and acceptor potential E(A/A−), a library of polyfluoro-substituted 1,3-diaryl-5-phenyl-pyrazolines was synthesized and characterized. The observed trends for the PET parameters were effectively captured through multiple Hammett linear free energy relationships (LFER) using a set of independent substituent constants for each of the two aryl rings. Given the lack of experimental Hammett constants for polyfluoro substituted aromatics, theoretically derived constants based on the electrostatic potential at the nucleus (EPN) of carbon atoms were employed as quantum chemical descriptors. The performance of the LFER was evaluated with a set of compounds that were not included in the training set, yielding a mean unsigned error of 0.05 eV for the prediction of the combined PET parameters. The outlined LFER approach should be well suited to design and optimize the performance of cation-responsive 1,3,5-triarylpyrazolines.
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影响因子：
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Kollmannsberger, M;Rurack, K;Daub, J
通讯作者：
Daub, J
影响因子：
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Gross, KC;Seybold, PG;Politzer, P
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Hirano, T;Kikuchi, K;Nagano, T
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Nagano, T
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Fahrni, CJ;Yang, LC;VanDerveer, DG
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VanDerveer, DG