Please use this identifier to cite or link to this item:
http://hdl.handle.net/1942/19151
Title: | Origin of the Individual Basicity of Corrole NH-Tautomers: A Quantum Chemical Study on Molecular Structure and Dynamics, Kinetics, and Thermodynamics | Authors: | Beenken, Wichard MAES, Wouter Kruk, Mikalai Martinez, Todd Presselt, Martin |
Issue Date: | 2015 | Publisher: | AMER CHEMICAL SOC | Source: | JOURNAL OF PHYSICAL CHEMISTRY A, 119 (26), p. 6875-6883 | Abstract: | Free-base corroles exist as individual NH-tautomers that may differ in their spectral and chemical properties. The present paper focuses on the origin of the basicity difference between two AB(2)-pyrimidinylcorrole NH-tautomers, which has been tentatively attributed to differences in the weak out-of-plane distortions of the pyrrolenic ring between two NH-tautomers. Using DFT-geometry optimizations, we show that the pyrroles involved in the NH-tautomerization process are approximately in-plane, whereas the other two pyrroles are tilted out-of-plane in opposite directions. Alternative out-of-plane distortion patterns play a minor role, as revealed by ab initio molecular dynamics simulations. Given that the protonated corrole is a unique species, the energy difference between the two NH-tautomers equals the difference in protonation driving force between them. This energy difference increases with improved theoretical level of accounting for intermolecular interactions and dielectric screening of surface charges. The different charge distributions of the two NH-tautomers result in electrostatic potential distributions that effect a larger proton attraction in the case of the T1 tautomer than in the case of the T2 tautomer. In summary, our quantum chemical results show clearly a higher basicity of the T1 tautomer as compared to the T2 tautomer: The previously assumed pronounced out-of-plane tilt of the Ti-nonprotonated nitrogen is verified by ab initio molecular dynamics simulations. Together with analysis of the electrostatic potential distribution we show that the nonprotonated nitrogen is not only tilted stronger but also significantly more accessible for protons in the case of Ti as compared to T2. Additionally, the thermodynamic basicity is higher for Ti than for T2. | Notes: | [Beenken, Wichard; Presselt, Martin] Ilmenau Univ Technol, Inst Phys, D-98684 Ilmenau, Germany. [Maes, Wouter] Hasselt Univ, Inst Mat Res IMO, Design & Synth Organ Semicond DSOS, B-3590 Diepenbeek, Belgium. [Kruk, Mikalai] Belarusian State Technol Univ, Dept Phys, Minsk 220006, Byelarus. [Martinez, Todd; Presselt, Martin] Stanford Univ, Dept Chem, Stanford, CA 94305 USA. [Martinez, Todd; Presselt, Martin] Stanford Univ, PULSE Inst, Stanford, CA 94305 USA. [Presselt, Martin] Univ Jena, Inst Phys Chem, D-07743 Jena, Germany. | Document URI: | http://hdl.handle.net/1942/19151 | ISSN: | 1089-5639 | e-ISSN: | 1520-5215 | DOI: | 10.1021/acs.jpca.5b02869 | ISI #: | 000357623600013 | Rights: | © 2015 American Chemical Society | Category: | A1 | Type: | Journal Contribution | Validations: | ecoom 2016 |
Appears in Collections: | Research publications |
Files in This Item:
File | Description | Size | Format | |
---|---|---|---|---|
acs%2Ejpca%2E5b02869.pdf Restricted Access | 4.23 MB | Adobe PDF | View/Open Request a copy |
SCOPUSTM
Citations
11
checked on Sep 3, 2020
WEB OF SCIENCETM
Citations
19
checked on Apr 30, 2024
Page view(s)
62
checked on Apr 26, 2023
Download(s)
46
checked on Apr 26, 2023
Google ScholarTM
Check
Altmetric
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.