Theoretical studies on the structures and optical properties of mono-phosphorus-substituted porphyrin/corrole compounds

单磷取代卟啉/咔咯化合物结构和光学性质理论研究

In this study,density functional theory(DFT)and time-dependent density functional theory(TD-DFT)were used to investigate the effects of phosphorus atoms on intramolecular hydrogen bonds,charge distribution,frontier orbitals,and electronic absorption spectrum peaks of phosphoheteroporphyrins(PP)and phosphoheterocorroles(PC).The data showed that the phosphorus site in the phosphorus porphyrin/corrole significantly lowered the highest occupied molecular orbital(HOMO)energy level and energy gap.The orbital energy levels of HOMO and HOMO-2 in PP21 and PC24 exhibited an elevation than that of the corresponding orbital energy levels of porphyrin/corrole,which facilitated the electron transition from the HOMO-2 to the lowest unoccupied molecular orbital and long-wavelength light absorption.In solvent conditions,the absorption wavelength of monophosphoporphyrins/monophosphocorroles exhibited significant redshift and were positively correlated with the decrease in solvent polarity.The results indicated that phosphoheteroporphyrin PP21 and phosphoheterocorrole PC24 had excellent electronic absorption spectra wavelengths in the visible light range,and might have a wide range of optoelectronic application potential.The above research data provided theoretical support for the screening and synthesis of heteroporphyrins and heterocorroles.

采用密度泛函理论和含时密度泛函理论研究了磷原子对磷杂卟啉(PP)和磷杂咔咯(PC)分子内氢键、电荷分布、前沿轨道和电子吸收谱峰的影响。数据表明,磷杂卟啉/咔咯中的磷位点显著降低了最高占据分子轨道(HOMO)的能级和能隙。与卟啉/咔咯相同的轨道能级相比,PP21和PC24的HOMO和HOMO-2轨道能级增加,使得HOMO-2轨道上的电子更容易跃迁到LUMO轨道,在吸收光谱中会出现新的长波吸收峰。在溶剂条件下,单磷杂卟啉/咔咯络合物的吸收波长表现出明显的红移,且与溶剂极性的降低呈正相关。结果表明,磷杂卟啉PP21和磷杂咔咯PC24在可见光范围内具有优异的电子吸收光谱波长,具有广泛的光电应用潜力。以上研究数据为杂卟啉和杂配物的筛选和合成提供了理论支持。