Supramolecular Chirogenesis in Bis-Porphyrin: Crystallographic Structure and CD Spectra for a Complex with a Chiral Guanidine Derivative
The complexation of (3a<i>R</i>,7a<i>R</i>)-<i>N</i>-(3,5-bis(trifluoromethyl)phenyl)octahydro-2<i>H</i>-benzo[<i>d</i>]imidazol-2-imine (BTI), as a guest, to ethane-bridged bis(zinc octaethylporphyrin), bis(ZnOEP), as a host, has been stud...
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MDPI AG
2021-02-01
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| Online Access: | https://www.mdpi.com/2073-8994/13/2/275 |
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| author | Irina Osadchuk Nele Konrad Khai-Nghi Truong Kari Rissanen Eric Clot Riina Aav Dzmitry Kananovich Victor Borovkov |
| author_facet | Irina Osadchuk Nele Konrad Khai-Nghi Truong Kari Rissanen Eric Clot Riina Aav Dzmitry Kananovich Victor Borovkov |
| author_sort | Irina Osadchuk |
| collection | DOAJ |
| description | The complexation of (3a<i>R</i>,7a<i>R</i>)-<i>N</i>-(3,5-bis(trifluoromethyl)phenyl)octahydro-2<i>H</i>-benzo[<i>d</i>]imidazol-2-imine (BTI), as a guest, to ethane-bridged bis(zinc octaethylporphyrin), bis(ZnOEP), as a host, has been studied by means of ultraviolet-visible (UV-Vis) and circular dichroism (CD) absorption spectroscopies, single crystal X-ray diffraction, and computational simulation. The formation of 1:2 host-guest complex was established by X-ray diffraction and UV-Vis titration studies. Two guest BTI molecules are located at the opposite sides of two porphyrin subunits of bis(ZnOEP) host, which is resting in the <i>anti</i>-conformation. The complexation of BTI molecules proceed via coordination of the imine nitrogens to the zinc ions of each porphyrin subunit of the host. Such supramolecular organization of the complex results in a screw arrangement of the two porphyrin subunits, inducing a strong CD signal in the Soret (B) band region. The corresponding DFT computational studies are in a good agreement with the experimental results and prove the presence of 1:2 host-guest complex as the major component in the solution (97.7%), but its optimized geometry differs from that observed in the solid-state. The UV-Vis and CD spectra simulated by using the solution-state geometry and the TD-DFT/ωB97X-D/cc-pVDZ + SMD (CH2Cl2) level of theory reproduced the experimentally obtained UV-Vis and CD spectra and confirmed the difference between the solid-state and solution structures. Moreover, it was shown that CD spectrum is very sensitive to the spatial arrangement of porphyrin subunits. |
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| institution | Directory Open Access Journal |
| issn | 2073-8994 |
| language | English |
| last_indexed | 2024-03-09T05:29:03Z |
| publishDate | 2021-02-01 |
| publisher | MDPI AG |
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| series | Symmetry |
| spelling | doaj.art-26bf84b5b2f34b1797821b8b57cb0b702023-12-03T12:33:50ZengMDPI AGSymmetry2073-89942021-02-0113227510.3390/sym13020275Supramolecular Chirogenesis in Bis-Porphyrin: Crystallographic Structure and CD Spectra for a Complex with a Chiral Guanidine DerivativeIrina Osadchuk0Nele Konrad1Khai-Nghi Truong2Kari Rissanen3Eric Clot4Riina Aav5Dzmitry Kananovich6Victor Borovkov7School of Science, Department of Chemistry and Biotechnology, Tallinn University of Technology, Akadeemia tee 15, 12618 Tallinn, EstoniaSchool of Science, Department of Chemistry and Biotechnology, Tallinn University of Technology, Akadeemia tee 15, 12618 Tallinn, EstoniaDepartment of Chemistry, University of Jyväskylä, P.O. Box 35, Survontie 9B, 40014 Jyväskylä, FinlandDepartment of Chemistry, University of Jyväskylä, P.O. Box 35, Survontie 9B, 40014 Jyväskylä, FinlandICGM, University Montpellier, CNRS, ENSCM, 34000 Montpellier, FranceSchool of Science, Department of Chemistry and Biotechnology, Tallinn University of Technology, Akadeemia tee 15, 12618 Tallinn, EstoniaSchool of Science, Department of Chemistry and Biotechnology, Tallinn University of Technology, Akadeemia tee 15, 12618 Tallinn, EstoniaSchool of Science, Department of Chemistry and Biotechnology, Tallinn University of Technology, Akadeemia tee 15, 12618 Tallinn, EstoniaThe complexation of (3a<i>R</i>,7a<i>R</i>)-<i>N</i>-(3,5-bis(trifluoromethyl)phenyl)octahydro-2<i>H</i>-benzo[<i>d</i>]imidazol-2-imine (BTI), as a guest, to ethane-bridged bis(zinc octaethylporphyrin), bis(ZnOEP), as a host, has been studied by means of ultraviolet-visible (UV-Vis) and circular dichroism (CD) absorption spectroscopies, single crystal X-ray diffraction, and computational simulation. The formation of 1:2 host-guest complex was established by X-ray diffraction and UV-Vis titration studies. Two guest BTI molecules are located at the opposite sides of two porphyrin subunits of bis(ZnOEP) host, which is resting in the <i>anti</i>-conformation. The complexation of BTI molecules proceed via coordination of the imine nitrogens to the zinc ions of each porphyrin subunit of the host. Such supramolecular organization of the complex results in a screw arrangement of the two porphyrin subunits, inducing a strong CD signal in the Soret (B) band region. The corresponding DFT computational studies are in a good agreement with the experimental results and prove the presence of 1:2 host-guest complex as the major component in the solution (97.7%), but its optimized geometry differs from that observed in the solid-state. The UV-Vis and CD spectra simulated by using the solution-state geometry and the TD-DFT/ωB97X-D/cc-pVDZ + SMD (CH2Cl2) level of theory reproduced the experimentally obtained UV-Vis and CD spectra and confirmed the difference between the solid-state and solution structures. Moreover, it was shown that CD spectrum is very sensitive to the spatial arrangement of porphyrin subunits.https://www.mdpi.com/2073-8994/13/2/275porphyringuanidinehost–guest bindingchiralitysupramolecular chemistrycircular dichroism |
| spellingShingle | Irina Osadchuk Nele Konrad Khai-Nghi Truong Kari Rissanen Eric Clot Riina Aav Dzmitry Kananovich Victor Borovkov Supramolecular Chirogenesis in Bis-Porphyrin: Crystallographic Structure and CD Spectra for a Complex with a Chiral Guanidine Derivative Symmetry porphyrin guanidine host–guest binding chirality supramolecular chemistry circular dichroism |
| title | Supramolecular Chirogenesis in Bis-Porphyrin: Crystallographic Structure and CD Spectra for a Complex with a Chiral Guanidine Derivative |
| title_full | Supramolecular Chirogenesis in Bis-Porphyrin: Crystallographic Structure and CD Spectra for a Complex with a Chiral Guanidine Derivative |
| title_fullStr | Supramolecular Chirogenesis in Bis-Porphyrin: Crystallographic Structure and CD Spectra for a Complex with a Chiral Guanidine Derivative |
| title_full_unstemmed | Supramolecular Chirogenesis in Bis-Porphyrin: Crystallographic Structure and CD Spectra for a Complex with a Chiral Guanidine Derivative |
| title_short | Supramolecular Chirogenesis in Bis-Porphyrin: Crystallographic Structure and CD Spectra for a Complex with a Chiral Guanidine Derivative |
| title_sort | supramolecular chirogenesis in bis porphyrin crystallographic structure and cd spectra for a complex with a chiral guanidine derivative |
| topic | porphyrin guanidine host–guest binding chirality supramolecular chemistry circular dichroism |
| url | https://www.mdpi.com/2073-8994/13/2/275 |
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