Huang Chun-Hao, Wu Chi-Chi, Li Elise Y, Chou Pi-Tai
Department of Chemistry, National Taiwan Normal University, Taipei, 11677, Taiwan.
Department of Chemistry, National Taiwan University, Taipei, 10617, Taiwan.
Phys Chem Chem Phys. 2023 Mar 29;25(13):9115-9122. doi: 10.1039/d3cp00298e.
In this study, we explore the possibilities of the deactivating pathways of organic thione containing systems through first-principles calculations. We particularly pay attention to the second lying singlet excited state, S, due to its large energy difference from the lowest lying S state in the sulfur-containing systems. Several theoretical models including the previously synthesized thiones and the strategically designed molecules are investigated to search for the basic conjugation unit that exhibits the prospect of S fission. Various molecular motifs and different substituents are combined to maneuver the relative alignment of the relevant low excited energy states. The results lead us to conclude that the thione derivatives, under rational and delicate molecular designs, may be engineered to possess a sufficiently high S-S energy gap as high as 2 eV and that these systems may exhibit S fission to triplet excitons in the red to near infrared region.
在本研究中，我们通过第一性原理计算探索了含有机硫酮体系失活途径的可能性。我们特别关注第二激发单重态S，因为它与含硫体系中最低激发的S态能量差很大。研究了包括先前合成的硫酮和经策略设计的分子在内的几种理论模型，以寻找具有S裂变前景的基本共轭单元。将各种分子基序和不同取代基结合起来，以操控相关低激发能态的相对排列。结果使我们得出结论，在合理而精细的分子设计下，硫酮衍生物可以被设计成具有高达2 eV的足够高的S-S能隙，并且这些体系可能在红色到近红外区域表现出向三重态激子的S裂变。
