Cristian Guerra, Yeray A. Rodríguez-Núñez, Manuel E. Taborda-Martínez, Mitchell Bacho, Rafael Miranda-Pastrana and Adolfo E. Ensuncho
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引用次数: 0
摘要
在本研究中,我们采用 ab initio 方法研究了取代α-托品的 4π 光环化过程。我们的研究结果表明,该反应的初始阶段发生在 S2 和 S3 等低能激发态,因为高能激发态的势垒过高。此外,我们还观察到,酸催化剂的存在或用电子捐献基团取代托品酮会降低能垒。关于双环[3.2.0]庚-3,6-二烯-2-酮衍生物的形成,T1/S0 和 S1/S0 交叉被认为是该失活过程的合理途径。具体来说,在返回基态的过程中,滋养酮上的电子捐献基团会促进 S1 和 S0 状态之间的变性。此外,在所有研究过的情况中,都观察到了 T1/S0 交叉系统。
Theoretical exploration of the 4π-photocyclization mechanism of α-tropone derivatives†
In this study, we employed ab initio methods to investigate the 4π-photocyclization process of substituted α-tropones. Our findings suggest that the initial stages of this reaction occur from low-energy excited states such as S2 and S3, as the barriers in higher-energy excited states are prohibitively high. Additionally, we observed that the presence of acid catalysts or substitution of tropones with electron-donating groups reduces the energy barriers. Regarding the formation of bicyclo[3.2.0]hepta-3,6-dien-2-one derivatives, both T1/S0 and S1/S0 crossings were identified as plausible pathways for this deactivation process. Specifically, electron-donating groups on the tropones promote degeneracy between S1 and S0 states during the return to the ground state. Moreover, T1/S0 crossing systems were consistently observed across all investigated scenarios.