Ji Yu, Moles Quintero Sergio, Dai Yasi, Marín-Beloqui Jose M, Zhang Hanjun, Zhan Qian, Sun Fanxi, Wang Dongsheng, Li Xiangkun, Wang Zhiyi, Gu Xinggui, Negri Fabrizia, Casado Juan, Zheng Yonghao
School of Optoelectronic Science and Engineering, University of Electronic Science and Technology of China (UESTC), Chengdu, 610054, P. R. China.
Department of Physical Chemistry, University of Málaga, Campus de Teatinos s/n, 29071, Málaga, Spain.
Angew Chem Int Ed Engl. 2023 Oct 16;62(42):e202311387. doi: 10.1002/anie.202311387. Epub 2023 Sep 12.
Diradicals based on the Blatter units and connected by acetylene and alkene spacers have been prepared. All the molecules show sizably large diradical character and low energy singlet-triplet gaps. Their photo-physical properties concerning their lowest energy excited state have been studied in detail by steady-state and time-resolved absorption spectroscopy. We have fully identified the main optical absorption band and full absence of emission from the lowest energy excited state. A computational study has been also carried out that has helped to identify the presence of a conical intersection between the lowest energy excited state and the ground state which produces a highly efficient light-to-heat conversion of the absorbed radiation. Furthermore, an outstanding photo-thermal conversion 77.23 % has been confirmed, close to the highest in the diradicaloid field. For the first time, stable diradicals are applied to photo-thermal therapy of tumor cells with good stability and satisfactory performance at near-infrared region.
基于布拉特单元并通过乙炔和烯烃间隔基相连的双自由基已被制备出来。所有分子都表现出相当大的双自由基特征和低能量的单重态-三重态能隙。通过稳态和时间分辨吸收光谱对它们关于最低能量激发态的光物理性质进行了详细研究。我们已完全确定了主要的光吸收带，并且最低能量激发态完全没有发射。还进行了一项计算研究，这有助于确定最低能量激发态与基态之间存在锥形交叉，这会导致吸收辐射的高效光热转换。此外，已证实具有77.23 %的出色光热转换率，接近双自由基类领域中的最高值。首次将稳定的双自由基应用于肿瘤细胞的光热治疗，在近红外区域具有良好的稳定性和令人满意的性能。
