Department of Chemistry and Chemical Technologies, Università della Calabria, 87036 Arcavacata di Rende, Italy.
ICGM, Univ. Montpellier, CNRS, ENSCM, 34293 Montpellier, France.
Molecules. 2022 Jun 23;27(13):4046. doi: 10.3390/molecules27134046.
The photophysical properties of two classes of porphyrins and metalloporphyrins linked to N-heterocyclic carbene (NHC) Au(I) complexes have been investigated by means of density functional theory and its time-dependent extension for their potential application in photodynamic therapy. For this purpose, the absorption spectra, the singlet-triplet energy gaps, and the spin-orbit coupling (SOC) constants have been determined. The obtained results show that all the studied compounds possess the appropriate properties to generate cytotoxic singlet molecular oxygen, and consequently, they can be employed as photosensitizers in photodynamic therapy. Nevertheless, on the basis of the computed SOCs and the analysis of the metal contribution to the involved molecular orbitals, a different influence in terms of the heavy atom effect in promoting the intersystem crossing process has been found as a function of the identity of the metal center and its position in the center of the porphyrin core or linked to the peripheral NHC.
两类卟啉和金属卟啉与 N-杂环卡宾 (NHC)Au(I) 配合物连接的光物理性质已通过密度泛函理论及其时间相关扩展进行了研究，以期将其潜在应用于光动力疗法。为此，确定了吸收光谱、单重态-三重态能隙和自旋轨道耦合 (SOC)常数。所得结果表明，所有研究的化合物都具有产生细胞毒性单重态分子氧的适当性质，因此，它们可用作光动力治疗中的光敏剂。然而，基于计算的 SOC 和对涉及分子轨道的金属贡献的分析，发现作为重原子效应在促进系间窜越过程中的不同影响取决于金属中心的身份及其在卟啉核心中心或连接到外围 NHC 的位置。
