Theoretical calculation on the substituent effect of strontium para-tetraphenyl porphyrins
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ORIGINAL RESEARCH
Theoretical calculation on the substituent effect of strontium para-tetraphenyl porphyrins Junping Du 1
&
Shanshan Feng 1 & Pengju Qin 1 & Yonghui Zhang 1 & Zhiqiang Zhang 1 & Liancai Xu 1
Received: 26 February 2020 / Accepted: 15 April 2020 # Springer Science+Business Media, LLC, part of Springer Nature 2020
Abstract A series of strontium para-tetraphenyl porphyrins (SrTRPPs) with different electron property substituents (R = -NH2, -OCH3, -H, -F, -COOH, -NO2) on the para-position of phenyl are designed. The substituent effect on their molecular structure, electronic structure, and stability and the electron absorption is investigated by density functional theory (DFT) method and time-dependent DFT (TDDFT) method. All SrTRPPs have dome-shaped configurations with the central metal Sr atom at the top of dome. The stronger electron withdrawing substituent induces the size of the dome smaller. All of them tend to form dimer or polymer. Strong electron-donating or electron-withdrawing substituent results the decrease of the band gaps and the excited state life. The binding energies, natural charge distribution, and intramolecular interaction research all show that the electron-withdrawing substituent is better for the stability of SrTRPPs. Meanwhile, a significant red shift of Q band has been found since the substituent decrease the aromatic properties of SrTRPPs. The strong electron-donating property of the substituent leads to increase in the intensity of absorption between 450 and 550 nm of SrTRPPs. It shows that the substituent effect is an efficient method to tune the structure and the properties of SrTRPPs. Keywords Strontium para-tetraphenyl porphyrins (SrTRPPs) . Substituent effect . Molecular structure . Electronic structure . Stability . Theoretical calculation
Introduction In the past decades, metalloporphyrins have been paid much more attention since its unique structure and properties [1–7]. Their tetrapyrrole conjugated macrocycles not only donate them a naturally universal coordinating ability which can complex most kinds of metal ions but also make itself have the self-adjusting ability by the structure modification. Metalloporphyrins have already shown an attractive application prospect in many fields such as dye-sensitizer [8–16], gas Electronic supplementary material The online version of this article (https://doi.org/10.1007/s11224-020-01539-3) contains supplementary material, which is available to authorized users. * Junping Du [email protected] * Liancai Xu [email protected] 1
College of Material and Chemical Engineering, Zhengzhou University of Light Industry, 5 Dongfeng Road, Zhengzhou, Henan Province 450002, People’s Republic of China
and biosensor [17, 18], catalysts [19–21], novel photoelectronic functional materials [8, 22–25], and molecular machines [26, 27]. There are two ways to modify the structure of metalloporphyrins. One is to change the metal ions. Their properties can be tuned and/or optimized by changing the size and formal charge of the complexing met
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