A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
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-tekijät tai -toimittajat

Julkaisun tiedot

Julkaisun kaikki tekijät tai toimittajat: Osadchuk, Irina; Konrad, Nele; Truong, Khai-Nghi; Rissanen, Kari; Clot, Eric; Aav, Riina; Kananovich, Dzmitry; Borovkov, Victor

Lehti tai sarja: Symmetry

eISSN: 2073-8994

Julkaisuvuosi: 2021

Ilmestymispäivä: 05.02.2021

Volyymi: 13

Lehden numero: 2

Artikkelinumero: 275

Kustantaja: MDPI AG

Julkaisumaa: Sveitsi

Julkaisun kieli: englanti

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

Julkaisun avoin saatavuus: Avoimesti saatavilla

Julkaisukanavan avoin saatavuus: Kokonaan avoin julkaisukanava

Julkaisu on rinnakkaistallennettu (JYX): https://jyx.jyu.fi/handle/123456789/74509

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


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.

YSO-asiasanat: supramolekulaarinen kemia; tiheysfunktionaaliteoria; kemialliset sidokset

Vapaat asiasanat: porphyrin; guanidine; host-guest binding; chirality; circular dichroism; DFT; TD-DFT simulation

Liittyvät organisaatiot


Hankkeet, joissa julkaisu on tehty

OKM-raportointi: Kyllä

Raportointivuosi: 2021

JUFO-taso: 1

Viimeisin päivitys 2022-14-09 klo 12:10