A Combined Experimental and Theoretical Study of ESR Hyperfine Coupling Constants for <i>N,N,N’,N’</i>-Tetrasubstituted <i>p</i>-Phenylenediamine Radical Cations
A test set of <i>N,N,N’,N’</i>-tetrasubstituted <i>p</i>-phenylenediamines are experimentally explored using ESR (electron spin resonance) spectroscopy and analysed from a computational standpoint thereafter. This computational study aims to further aid structural characteris...
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MDPI AG
2023-02-01
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| Series: | International Journal of Molecular Sciences |
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| Online Access: | https://www.mdpi.com/1422-0067/24/4/3447 |
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| author | Ronan Gleeson Cecilie L. Andersen Peter Rapta Peter Machata Jørn B. Christensen Ole Hammerich Stephan P. A. Sauer |
| author_facet | Ronan Gleeson Cecilie L. Andersen Peter Rapta Peter Machata Jørn B. Christensen Ole Hammerich Stephan P. A. Sauer |
| author_sort | Ronan Gleeson |
| collection | DOAJ |
| description | A test set of <i>N,N,N’,N’</i>-tetrasubstituted <i>p</i>-phenylenediamines are experimentally explored using ESR (electron spin resonance) spectroscopy and analysed from a computational standpoint thereafter. This computational study aims to further aid structural characterisation by comparing experimental ESR hyperfine coupling constants (hfccs) with computed values calculated using ESR-optimised “J-style” basis sets (6-31G(d,p)-J, 6-31G(d,p)-J, 6-311++G(d,p)-J, pcJ-1, pcJ-2 and cc-pVTZ-J) and hybrid-DFT functionals (B3LYP, PBE0, TPSSh, <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mi>ω</mi></semantics></math></inline-formula>B97XD) as well as MP2. PBE0/6-31g(d,p)-J with a polarised continuum solvation model (PCM) correlated best with the experiment, giving an <i>R</i><inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msup><mrow></mrow><mn>2</mn></msup></semantics></math></inline-formula> value of 0.8926. A total of 98% of couplings were deemed satisfactory, with five couplings observed as outlier results, thus degrading correlation values significantly. A higher-level electronic structure method, namely MP2, was sought to improve outlier couplings, but only a minority of couples showed improvement, whilst the remaining majority of couplings were negatively degraded. |
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| issn | 1661-6596 1422-0067 |
| language | English |
| last_indexed | 2024-03-11T08:43:24Z |
| publishDate | 2023-02-01 |
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| series | International Journal of Molecular Sciences |
| spelling | doaj.art-daae072c1f0943749ff49efe10495b362023-11-16T21:00:08ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672023-02-01244344710.3390/ijms24043447A Combined Experimental and Theoretical Study of ESR Hyperfine Coupling Constants for <i>N,N,N’,N’</i>-Tetrasubstituted <i>p</i>-Phenylenediamine Radical CationsRonan Gleeson0Cecilie L. Andersen1Peter Rapta2Peter Machata3Jørn B. Christensen4Ole Hammerich5Stephan P. A. Sauer6Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen, DenmarkDepartment of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen, DenmarkInstitute of Physical Chemistry and Chemical Physics, Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinského 9, 812 37 Bratislava, SlovakiaInstitute of Physical Chemistry and Chemical Physics, Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinského 9, 812 37 Bratislava, SlovakiaDepartment of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen, DenmarkDepartment of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen, DenmarkDepartment of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen, DenmarkA test set of <i>N,N,N’,N’</i>-tetrasubstituted <i>p</i>-phenylenediamines are experimentally explored using ESR (electron spin resonance) spectroscopy and analysed from a computational standpoint thereafter. This computational study aims to further aid structural characterisation by comparing experimental ESR hyperfine coupling constants (hfccs) with computed values calculated using ESR-optimised “J-style” basis sets (6-31G(d,p)-J, 6-31G(d,p)-J, 6-311++G(d,p)-J, pcJ-1, pcJ-2 and cc-pVTZ-J) and hybrid-DFT functionals (B3LYP, PBE0, TPSSh, <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mi>ω</mi></semantics></math></inline-formula>B97XD) as well as MP2. PBE0/6-31g(d,p)-J with a polarised continuum solvation model (PCM) correlated best with the experiment, giving an <i>R</i><inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msup><mrow></mrow><mn>2</mn></msup></semantics></math></inline-formula> value of 0.8926. A total of 98% of couplings were deemed satisfactory, with five couplings observed as outlier results, thus degrading correlation values significantly. A higher-level electronic structure method, namely MP2, was sought to improve outlier couplings, but only a minority of couples showed improvement, whilst the remaining majority of couplings were negatively degraded.https://www.mdpi.com/1422-0067/24/4/3447ESRorganic radicalsDFTJ-augmented basis sets |
| spellingShingle | Ronan Gleeson Cecilie L. Andersen Peter Rapta Peter Machata Jørn B. Christensen Ole Hammerich Stephan P. A. Sauer A Combined Experimental and Theoretical Study of ESR Hyperfine Coupling Constants for <i>N,N,N’,N’</i>-Tetrasubstituted <i>p</i>-Phenylenediamine Radical Cations International Journal of Molecular Sciences ESR organic radicals DFT J-augmented basis sets |
| title | A Combined Experimental and Theoretical Study of ESR Hyperfine Coupling Constants for <i>N,N,N’,N’</i>-Tetrasubstituted <i>p</i>-Phenylenediamine Radical Cations |
| title_full | A Combined Experimental and Theoretical Study of ESR Hyperfine Coupling Constants for <i>N,N,N’,N’</i>-Tetrasubstituted <i>p</i>-Phenylenediamine Radical Cations |
| title_fullStr | A Combined Experimental and Theoretical Study of ESR Hyperfine Coupling Constants for <i>N,N,N’,N’</i>-Tetrasubstituted <i>p</i>-Phenylenediamine Radical Cations |
| title_full_unstemmed | A Combined Experimental and Theoretical Study of ESR Hyperfine Coupling Constants for <i>N,N,N’,N’</i>-Tetrasubstituted <i>p</i>-Phenylenediamine Radical Cations |
| title_short | A Combined Experimental and Theoretical Study of ESR Hyperfine Coupling Constants for <i>N,N,N’,N’</i>-Tetrasubstituted <i>p</i>-Phenylenediamine Radical Cations |
| title_sort | combined experimental and theoretical study of esr hyperfine coupling constants for i n n n n i tetrasubstituted i p i phenylenediamine radical cations |
| topic | ESR organic radicals DFT J-augmented basis sets |
| url | https://www.mdpi.com/1422-0067/24/4/3447 |
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