De Simone B C, Mazzone G, Pirillo J, Russo N, Sicilia E
Dipartimento di Chimica e Tecnologie Chimiche, Università della Calabria, I-87036 Arcavacata di Rende, Italy.
Phys Chem Chem Phys. 2017 Jan 18;19(3):2530-2536. doi: 10.1039/c6cp07874e.
The influence of halogen atom substitution (Br and I), in different amounts and positions in an aza-BODIPY skeleton, on the photophysical properties of some aza-BODIPY derivatives has been investigated by using density functional theory and its time-dependent extension. The heavy atom effect on excitation energies, singlet-triplet energy gaps and spin-orbit matrix elements has been considered. The maximum absorption within the therapeutic window has been confirmed for all the aza-BODIPY derivatives. The feasible intersystem spin crossing pathways for the population of the lowest triplet state, that will depend on the values of the spin-orbit matrix elements, the energy gap as well as the orbital composition of the involved states have been found to most likely involve the S and T or T states. The outcomes of computations support the potential therapeutic use of these compounds as photosensitizers in photodynamic therapy.
通过使用密度泛函理论及其含时扩展，研究了氮杂-BODIPY骨架中不同数量和位置的卤素原子取代（Br和I）对一些氮杂-BODIPY衍生物光物理性质的影响。考虑了重原子对激发能、单重态-三重态能隙和自旋-轨道矩阵元的影响。已证实所有氮杂-BODIPY衍生物在治疗窗口内具有最大吸收。已发现，对于最低三重态的布居，可行的系间自旋交叉途径很可能涉及S和T或T态，这取决于自旋-轨道矩阵元的值、能隙以及相关态的轨道组成。计算结果支持这些化合物作为光动力疗法中光敏剂的潜在治疗用途。
