A1 Journal article (refereed)
Supramolecular Chirogenesis in Bis-Porphyrin : Crystallographic Structure and CD Spectra for a Complex with a Chiral Guanidine Derivative (2021)

Osadchuk, I., Konrad, N., Truong, K.-N., Rissanen, K., Clot, E., Aav, R., Kananovich, D., & Borovkov, V. (2021). Supramolecular Chirogenesis in Bis-Porphyrin : Crystallographic Structure and CD Spectra for a Complex with a Chiral Guanidine Derivative. Symmetry, 13(2), Article 275. https://doi.org/10.3390/sym13020275

JYU authors or editors

Publication details

All authors or editors: Osadchuk, Irina; Konrad, Nele; Truong, Khai-Nghi; Rissanen, Kari; Clot, Eric; Aav, Riina; Kananovich, Dzmitry; Borovkov, Victor

Journal or series: Symmetry

eISSN: 2073-8994

Publication year: 2021

Publication date: 05/02/2021

Volume: 13

Issue number: 2

Article number: 275

Publisher: MDPI AG

Publication country: Switzerland

Publication language: English

DOI: https://doi.org/10.3390/sym13020275

Publication open access: Openly available

Publication channel open access: Open Access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/74509

Additional information: This article belongs to the Special Issue Chiral Auxiliaries and Chirogenesis II.

Abstract

The complexation of (3aR,7aR)-N-(3,5-bis(trifluoromethyl)phenyl)octahydro-2H-benzo[d]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 anti-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.

Keywords: supramolecular chemistry; density functional theory; chemical bonds

Free keywords: porphyrin; guanidine; host-guest binding; chirality; circular dichroism; DFT; TD-DFT simulation

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Ministry reporting: Yes

Reporting Year: 2021

JUFO rating: 1