Self-assembly of supramolecular architectures driven by σ-hole interactions: a halogen-bonded 2d network based on a diiminedibromido gold(III) complex and tribromide building blocks

M Carla Aragoni; M Francesca Cherchi; Vito Lippolis; Anna Pintus; Enrico Podda; Alexandra M Z Slawin; J Derek Woollins; Massimiliano Arca

doi:10.3390/molecules27196289

Self-assembly of supramolecular architectures driven by σ-hole interactions: a halogen-bonded 2d network based on a diiminedibromido gold(III) complex and tribromide building blocks

M Carla Aragoni, M Francesca Cherchi, Vito Lippolis, Anna Pintus, Enrico Podda, Alexandra M Z Slawin, J Derek Woollins, Massimiliano Arca^*

^*Corresponding author for this work

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

Abstract

The reaction of the complex [Au(phen)Br₂](PF₆) (phen = 1,10-phenanthroline) with molecular dibromine afforded {[Au(phen)Br₂](Br₃)}_∞ (1). Single crystal diffraction analysis showed that the [Au(phen)Br₂]⁺ complex cations were bridged by asymmetric tribromide anions to form infinite zig-zag chains featuring the motif ···Au–Br···Br–Br–Br···Au–Br···Br–Br–Br···. The complex cation played an unprecedented halogen bonding (XB) donor role engaging type-I and type-II XB noncovalent interactions of comparable strength with symmetry related [Br₃]⁻ anions. A network of hydrogen bonds connects parallel chains in an infinite 2D network, contributing to the layered supramolecular architecture. DFT calculations allowed clarification of the nature of the XB interactions, showing the interplay between orbital mixing, analyzed at the NBO level, and electrostatic contribution, explored based on the molecular potential energy (MEP) maps of the interacting synthons.

Original language	English
Article number	6289
Number of pages	9
Journal	Molecules
Volume	27
Issue number	19
DOIs	https://doi.org/10.3390/molecules27196289
Publication status	Published - 23 Sept 2022

Keywords

Supramolecular
Bromine
Sigma-hole
Halogen bond
Crystallography
Gold
Polyhalide
DFT

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Copyright: © 2022 by the authors. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https:// creativecommons.org/licenses/by/4.0/).
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Aragoni, M. C., Cherchi, M. F., Lippolis, V., Pintus, A., Podda, E., Slawin, A. M. Z., Woollins, J. D., & Arca, M. (2022). Self-assembly of supramolecular architectures driven by σ-hole interactions: a halogen-bonded 2d network based on a diiminedibromido gold(III) complex and tribromide building blocks. Molecules, 27(19), Article 6289. https://doi.org/10.3390/molecules27196289

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title = "Self-assembly of supramolecular architectures driven by σ-hole interactions: a halogen-bonded 2d network based on a diiminedibromido gold(III) complex and tribromide building blocks",

abstract = "The reaction of the complex [Au(phen)Br2](PF6) (phen = 1,10-phenanthroline) with molecular dibromine afforded {[Au(phen)Br2](Br3)}∞ (1). Single crystal diffraction analysis showed that the [Au(phen)Br2]+ complex cations were bridged by asymmetric tribromide anions to form infinite zig-zag chains featuring the motif ···Au–Br···Br–Br–Br···Au–Br···Br–Br–Br···. The complex cation played an unprecedented halogen bonding (XB) donor role engaging type-I and type-II XB noncovalent interactions of comparable strength with symmetry related [Br3]− anions. A network of hydrogen bonds connects parallel chains in an infinite 2D network, contributing to the layered supramolecular architecture. DFT calculations allowed clarification of the nature of the XB interactions, showing the interplay between orbital mixing, analyzed at the NBO level, and electrostatic contribution, explored based on the molecular potential energy (MEP) maps of the interacting synthons.",

keywords = "Supramolecular, Bromine, Sigma-hole, Halogen bond, Crystallography, Gold, Polyhalide, DFT",

author = "Aragoni, {M Carla} and Cherchi, {M Francesca} and Vito Lippolis and Anna Pintus and Enrico Podda and Slawin, {Alexandra M Z} and Woollins, {J Derek} and Massimiliano Arca",

note = "Funding: The authors acknowledge Fondazione di Sardegna (FdS Progetti Biennali di Ateneo, annualit{\`a} 2018) for the financial support.",

year = "2022",

month = sep,

day = "23",

doi = "10.3390/molecules27196289",

language = "English",

volume = "27",

journal = "Molecules",

issn = "1420-3049",

publisher = "Multidisciplinary Digital Publishing Institute (MDPI)",

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T1 - Self-assembly of supramolecular architectures driven by σ-hole interactions

T2 - a halogen-bonded 2d network based on a diiminedibromido gold(III) complex and tribromide building blocks

AU - Aragoni, M Carla

AU - Cherchi, M Francesca

AU - Lippolis, Vito

AU - Pintus, Anna

AU - Podda, Enrico

AU - Slawin, Alexandra M Z

AU - Woollins, J Derek

AU - Arca, Massimiliano

N1 - Funding: The authors acknowledge Fondazione di Sardegna (FdS Progetti Biennali di Ateneo, annualità 2018) for the financial support.

PY - 2022/9/23

Y1 - 2022/9/23

N2 - The reaction of the complex [Au(phen)Br2](PF6) (phen = 1,10-phenanthroline) with molecular dibromine afforded {[Au(phen)Br2](Br3)}∞ (1). Single crystal diffraction analysis showed that the [Au(phen)Br2]+ complex cations were bridged by asymmetric tribromide anions to form infinite zig-zag chains featuring the motif ···Au–Br···Br–Br–Br···Au–Br···Br–Br–Br···. The complex cation played an unprecedented halogen bonding (XB) donor role engaging type-I and type-II XB noncovalent interactions of comparable strength with symmetry related [Br3]− anions. A network of hydrogen bonds connects parallel chains in an infinite 2D network, contributing to the layered supramolecular architecture. DFT calculations allowed clarification of the nature of the XB interactions, showing the interplay between orbital mixing, analyzed at the NBO level, and electrostatic contribution, explored based on the molecular potential energy (MEP) maps of the interacting synthons.

AB - The reaction of the complex [Au(phen)Br2](PF6) (phen = 1,10-phenanthroline) with molecular dibromine afforded {[Au(phen)Br2](Br3)}∞ (1). Single crystal diffraction analysis showed that the [Au(phen)Br2]+ complex cations were bridged by asymmetric tribromide anions to form infinite zig-zag chains featuring the motif ···Au–Br···Br–Br–Br···Au–Br···Br–Br–Br···. The complex cation played an unprecedented halogen bonding (XB) donor role engaging type-I and type-II XB noncovalent interactions of comparable strength with symmetry related [Br3]− anions. A network of hydrogen bonds connects parallel chains in an infinite 2D network, contributing to the layered supramolecular architecture. DFT calculations allowed clarification of the nature of the XB interactions, showing the interplay between orbital mixing, analyzed at the NBO level, and electrostatic contribution, explored based on the molecular potential energy (MEP) maps of the interacting synthons.

KW - Supramolecular

KW - Bromine

KW - Sigma-hole

KW - Halogen bond

KW - Crystallography

KW - Gold

KW - Polyhalide

KW - DFT

U2 - 10.3390/molecules27196289

DO - 10.3390/molecules27196289

M3 - Article

C2 - 36234826

SN - 1420-3049

VL - 27

JO - Molecules

JF - Molecules

IS - 19

M1 - 6289

ER -

Self-assembly of supramolecular architectures driven by σ-hole interactions: a halogen-bonded 2d network based on a diiminedibromido gold(III) complex and tribromide building blocks

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Keywords

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