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通过轴向氟化调节五价锑卟啉中的分子内电荷转移

Tuning Intramolecular Charge Transfer in Antimony(V) Porphyrin through Axial Fluorination.

作者信息

Holzer Noah, Sharma Jatan K, D'Souza Francis, Poddutoori Prashanth K

机构信息

Advanced Materials Center, University of Minnesota Duluth, 1405 University Drive, Duluth, Minnesota 55812, United States.

Department of Chemistry & Biochemistry, University of Minnesota Duluth, 1038 University Drive, Duluth, Minnesota 55812, United States.

出版信息

ACS Omega. 2024 May 13;9(21):22892-22902. doi: 10.1021/acsomega.4c01773. eCollection 2024 May 28.

DOI:10.1021/acsomega.4c01773
PMID:38826543
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11137685/
Abstract

Modulation of intramolecular charge transfer (ICT) has been tested in two antimony(V) porphyrins, SbT(DMP)P(OMe)·PF and SbT(DMP)P(OTFE)·PF, where the -positions are occupied by 3,5-dimethoxyphenyl (DMP), and the axial positions are linked with either methoxy (OMe) or trifluoroethoxy (OTFE) units, respectively. The presence of the Sb(+5) ion makes the porphyrin center electron poor. Under this situation, placing electron-rich units in the -position creates a condition for push-pull type ICT in the SbT(DMP)P(OMe)·PF. Remarkably, it is shown that the ICT character can be further enhanced in SbT(DMP)P(OTFE)·PF with the help of electron-withdrawing TFE units in the axial position, which makes the porphyrin center even more electron scarce. The steady-state and transient studies as well as solvatochromism studies establish the ICT in SbT(DMP)P(OMe)·PF and SbT(DMP)P(OTFE)·PF, and the strength of the ICT can be modulated by exploiting the structural properties of antimony(V) porphyrin. The existence of ICT is further supported by density functional theory calculations. The transient studies show that upon excitation of these porphyrin, their charge-transfer states convert to a full charger-separated states with appreciable lifetimes.

摘要

在两种五价锑卟啉SbT(DMP)P(OMe)·PF和SbT(DMP)P(OTFE)·PF中测试了分子内电荷转移(ICT)的调制，其中β-位被3,5-二甲氧基苯基(DMP)占据，轴向位置分别与甲氧基(OMe)或三氟乙氧基(OTFE)单元相连。Sb(+5)离子的存在使卟啉中心电子匮乏。在这种情况下，在β-位放置富电子单元为SbT(DMP)P(OMe)·PF中的推挽型ICT创造了条件。值得注意的是，结果表明，在轴向位置带有吸电子TFE单元的SbT(DMP)P(OTFE)·PF中，ICT特性可以进一步增强，这使得卟啉中心的电子更加稀缺。稳态和瞬态研究以及溶剂化显色研究证实了SbT(DMP)P(OMe)·PF和SbT(DMP)P(OTFE)·PF中存在ICT，并且可以通过利用五价锑卟啉的结构特性来调节ICT的强度。密度泛函理论计算进一步支持了ICT的存在。瞬态研究表明，在这些卟啉激发后，它们的电荷转移态会转变为具有可观寿命的完全电荷分离态。

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