Halogen Bonding and CO-Ligand Blue-Shift in Hybrid Organic—Organometallic Cocrystals [CpFe(CO)2X] (C2I4) (X = Cl, Br)

Yury Torubaev; Ivan Skabitskiy; Sergey Shapovalov; Olga Tikhonova; Anna Popova

doi:10.3390/cryst12030412

Halogen Bonding and CO-Ligand Blue-Shift in Hybrid Organic—Organometallic Cocrystals [CpFe(CO)₂X] (C₂I₄) (X = Cl, Br)

Yury Torubaev, Ivan Skabitskiy, Sergey Shapovalov, Olga Tikhonova, Anna Popova

Research output: Contribution to journal › Article › peer-review

1 Scopus citations

Abstract

This work is focused on the complex interplay of geometry of I· · · X halogen bonds (HaB) and intermolecular interaction energy in two isomorphic cocrystals [CpFe(CO)₂X] (C₂ I₄ ) (X = Cl (1), Br (2)). Their IR-spectroscopic measurements in solid state and solution demonstrate the blue-shift of CO vibration bands, resulting from I· · · X HaB. The reluctance of their iodide congener [CpFe(CO)₂ I] to form the expected cocrystal [CpFe(CO)₂ I] (C₂ I₄ ) is discussed in terms of different molecular electrostatic potential (MEP) of the surface of iodide ligands, as compared with chloride and bromide, which dictate a different angular geometry of HaB around the metal-I and metal-Br/Cl HaB acceptors. This study also suggests C₂ I₄ as a reliable HaB donor coformer for metal-halide HaB acceptors in the crystal engineering of hybrid metal–organic systems.

Original language	English
Article number	412
Journal	Crystals
Volume	12
Issue number	3
DOIs	https://doi.org/10.3390/cryst12030412
State	Published - 1 Mar 2022
Externally published	Yes

Keywords

blue-shift
cocrystal
halogen bonding
σ-hole

ASJC Scopus subject areas

General Chemical Engineering
General Materials Science
Condensed Matter Physics
Inorganic Chemistry

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.3390/cryst12030412

Cite this

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title = "Halogen Bonding and CO-Ligand Blue-Shift in Hybrid Organic—Organometallic Cocrystals [CpFe(CO)2X] (C2I4) (X = Cl, Br)",

abstract = "This work is focused on the complex interplay of geometry of I· · · X halogen bonds (HaB) and intermolecular interaction energy in two isomorphic cocrystals [CpFe(CO)2X] (C2 I4 ) (X = Cl (1), Br (2)). Their IR-spectroscopic measurements in solid state and solution demonstrate the blue-shift of CO vibration bands, resulting from I· · · X HaB. The reluctance of their iodide congener [CpFe(CO)2 I] to form the expected cocrystal [CpFe(CO)2 I] (C2 I4 ) is discussed in terms of different molecular electrostatic potential (MEP) of the surface of iodide ligands, as compared with chloride and bromide, which dictate a different angular geometry of HaB around the metal-I and metal-Br/Cl HaB acceptors. This study also suggests C2 I4 as a reliable HaB donor coformer for metal-halide HaB acceptors in the crystal engineering of hybrid metal–organic systems.",

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author = "Yury Torubaev and Ivan Skabitskiy and Sergey Shapovalov and Olga Tikhonova and Anna Popova",

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T1 - Halogen Bonding and CO-Ligand Blue-Shift in Hybrid Organic—Organometallic Cocrystals [CpFe(CO)2X] (C2I4) (X = Cl, Br)

AU - Torubaev, Yury

AU - Skabitskiy, Ivan

AU - Shapovalov, Sergey

AU - Tikhonova, Olga

AU - Popova, Anna

PY - 2022/3/1

Y1 - 2022/3/1

N2 - This work is focused on the complex interplay of geometry of I· · · X halogen bonds (HaB) and intermolecular interaction energy in two isomorphic cocrystals [CpFe(CO)2X] (C2 I4 ) (X = Cl (1), Br (2)). Their IR-spectroscopic measurements in solid state and solution demonstrate the blue-shift of CO vibration bands, resulting from I· · · X HaB. The reluctance of their iodide congener [CpFe(CO)2 I] to form the expected cocrystal [CpFe(CO)2 I] (C2 I4 ) is discussed in terms of different molecular electrostatic potential (MEP) of the surface of iodide ligands, as compared with chloride and bromide, which dictate a different angular geometry of HaB around the metal-I and metal-Br/Cl HaB acceptors. This study also suggests C2 I4 as a reliable HaB donor coformer for metal-halide HaB acceptors in the crystal engineering of hybrid metal–organic systems.

AB - This work is focused on the complex interplay of geometry of I· · · X halogen bonds (HaB) and intermolecular interaction energy in two isomorphic cocrystals [CpFe(CO)2X] (C2 I4 ) (X = Cl (1), Br (2)). Their IR-spectroscopic measurements in solid state and solution demonstrate the blue-shift of CO vibration bands, resulting from I· · · X HaB. The reluctance of their iodide congener [CpFe(CO)2 I] to form the expected cocrystal [CpFe(CO)2 I] (C2 I4 ) is discussed in terms of different molecular electrostatic potential (MEP) of the surface of iodide ligands, as compared with chloride and bromide, which dictate a different angular geometry of HaB around the metal-I and metal-Br/Cl HaB acceptors. This study also suggests C2 I4 as a reliable HaB donor coformer for metal-halide HaB acceptors in the crystal engineering of hybrid metal–organic systems.

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