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 or...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.展开更多
基金the financial support from the National Natural Science Foundation of China(21601025,21571025,21601024)Scientific Research Projects in Universities of Education Department of Liaoning Province(LJKQZ2021168)the Subject Construction Project-the Interdisciplinary Project of Dalian University(DLUXK-2023-YB-007)Scientific Research Platform Project of Dalian University(202101ZD01).
文摘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.
