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
The reaction of the complex [Au(phen)Br<sub>2</sub>](PF<sub>6</sub>) (phen = 1,10-phenanthroline) with molecular dibromine afforded {[Au(phen)Br<sub>2</sub>](Br<sub>3</sub>)}<sub>∞</sub> (<b>1</b>). Single crystal diffraction an...
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| Format: | Article |
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MDPI AG
2022-09-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/27/19/6289 |
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| author | M. Carla Aragoni M. Francesca Cherchi Vito Lippolis Anna Pintus Enrico Podda Alexandra M. Z. Slawin J. Derek Woollins Massimiliano Arca |
| author_facet | M. Carla Aragoni M. Francesca Cherchi Vito Lippolis Anna Pintus Enrico Podda Alexandra M. Z. Slawin J. Derek Woollins Massimiliano Arca |
| author_sort | M. Carla Aragoni |
| collection | DOAJ |
| description | The reaction of the complex [Au(phen)Br<sub>2</sub>](PF<sub>6</sub>) (phen = 1,10-phenanthroline) with molecular dibromine afforded {[Au(phen)Br<sub>2</sub>](Br<sub>3</sub>)}<sub>∞</sub> (<b>1</b>). Single crystal diffraction analysis showed that the [Au(phen)Br<sub>2</sub>]<sup>+</sup> 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 [Br<sub>3</sub>]<sup>−</sup> 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. |
| first_indexed | 2024-03-09T21:26:01Z |
| format | Article |
| id | doaj.art-c793a869ef4a496ab56c4229b2a32cbb |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T21:26:01Z |
| publishDate | 2022-09-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-c793a869ef4a496ab56c4229b2a32cbb2023-11-23T21:08:54ZengMDPI AGMolecules1420-30492022-09-012719628910.3390/molecules27196289Self-Assembly of Supramolecular Architectures Driven by σ-Hole Interactions: A Halogen-Bonded 2D Network Based on a Diiminedibromido Gold(III) Complex and Tribromide Building BlocksM. Carla Aragoni0M. Francesca Cherchi1Vito Lippolis2Anna Pintus3Enrico Podda4Alexandra M. Z. Slawin5J. Derek Woollins6Massimiliano Arca7Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, S.S. 554 bivio per Sestu, 09042 Monserrato, ItalyDipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, S.S. 554 bivio per Sestu, 09042 Monserrato, ItalyDipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, S.S. 554 bivio per Sestu, 09042 Monserrato, ItalyDipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, S.S. 554 bivio per Sestu, 09042 Monserrato, ItalyDipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, S.S. 554 bivio per Sestu, 09042 Monserrato, ItalyEaStCHEM School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, Fife KY16 9ST, UKEaStCHEM School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, Fife KY16 9ST, UKDipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, S.S. 554 bivio per Sestu, 09042 Monserrato, ItalyThe reaction of the complex [Au(phen)Br<sub>2</sub>](PF<sub>6</sub>) (phen = 1,10-phenanthroline) with molecular dibromine afforded {[Au(phen)Br<sub>2</sub>](Br<sub>3</sub>)}<sub>∞</sub> (<b>1</b>). Single crystal diffraction analysis showed that the [Au(phen)Br<sub>2</sub>]<sup>+</sup> 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 [Br<sub>3</sub>]<sup>−</sup> 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.https://www.mdpi.com/1420-3049/27/19/6289goldsupramolecularhalogen bondsigma-holecrystallographyDFT |
| spellingShingle | M. Carla Aragoni M. Francesca Cherchi Vito Lippolis Anna Pintus Enrico Podda Alexandra M. Z. Slawin J. Derek Woollins Massimiliano Arca 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 gold supramolecular halogen bond sigma-hole crystallography DFT |
| 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 |
| title_full | 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 |
| title_fullStr | 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 |
| title_full_unstemmed | 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 |
| title_short | 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 |
| title_sort | 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 |
| topic | gold supramolecular halogen bond sigma-hole crystallography DFT |
| url | https://www.mdpi.com/1420-3049/27/19/6289 |
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