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Conglomerate Aggregation of 7,12,17-Trioxa[11]helicene into Homochiral Two-Dimensional Crystals on the Cu(100) Surface


Irziqat, Bahaaeddin; Berger, Jan; Cebrat, Aleksandra; Mendieta‐Moreno, Jesús I; Sundar, Mothuku Shyam; Bedekar, Ashutosh V; Ernst, Karl‐Heinz (2022). Conglomerate Aggregation of 7,12,17-Trioxa[11]helicene into Homochiral Two-Dimensional Crystals on the Cu(100) Surface. Helvetica Chimica Acta, 105(12):e202200114.

Abstract

Despite the vast development of stereochemistry it remains a great challenge to predict the fate of homochiral or heterochiral recognition in crystallization from racemic solution or melt. Using the well-defined model system of racemic trioxaundecahelicene on a Cu(100) surface in ultrahigh vacuum, the chiral recognition of this heterohelicene has been investigated by means of state-of-the-art scanning probe microscopy. The combination of scanning tunneling microscopy and tuning fork-based non-contact atomic force microscopy allowed assignment of the absolute configuration of single 7,12,17-trioxa[11]helicene molecules in their two-dimensional assemblies. At very low coverages, homochiral van der Waals-bonded tetramers are observed. These also constitute the building blocks of the completely filled monolayer, which is a 2D conglomerate of homochiral domains. The interpretation of the adsorption geometries was supported by density-functional theory calculations and molecular dynamics simulations, predicting a stronger interaction energy for homochiral structures over the heterochiral assembly. The striking similarity to heptahelicene on the same surface suggests that chiral recognition is dominated by the footprint interaction of the molecules with the metallic substrate.

Abstract

Despite the vast development of stereochemistry it remains a great challenge to predict the fate of homochiral or heterochiral recognition in crystallization from racemic solution or melt. Using the well-defined model system of racemic trioxaundecahelicene on a Cu(100) surface in ultrahigh vacuum, the chiral recognition of this heterohelicene has been investigated by means of state-of-the-art scanning probe microscopy. The combination of scanning tunneling microscopy and tuning fork-based non-contact atomic force microscopy allowed assignment of the absolute configuration of single 7,12,17-trioxa[11]helicene molecules in their two-dimensional assemblies. At very low coverages, homochiral van der Waals-bonded tetramers are observed. These also constitute the building blocks of the completely filled monolayer, which is a 2D conglomerate of homochiral domains. The interpretation of the adsorption geometries was supported by density-functional theory calculations and molecular dynamics simulations, predicting a stronger interaction energy for homochiral structures over the heterochiral assembly. The striking similarity to heptahelicene on the same surface suggests that chiral recognition is dominated by the footprint interaction of the molecules with the metallic substrate.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > Catalysis
Life Sciences > Biochemistry
Life Sciences > Drug Discovery
Physical Sciences > Physical and Theoretical Chemistry
Physical Sciences > Organic Chemistry
Physical Sciences > Inorganic Chemistry
Uncontrolled Keywords:Inorganic Chemistry, Organic Chemistry, Physical and Theoretical Chemistry, Drug Discovery, Biochemistry, Catalysis
Language:English
Date:1 December 2022
Deposited On:17 Feb 2023 17:24
Last Modified:28 Apr 2024 01:49
Publisher:Wiley Open Access
ISSN:1522-2675
OA Status:Closed
Publisher DOI:https://doi.org/10.1002/hlca.202200114
Project Information:
  • : FunderH2020
  • : Grant ID820820
  • : Project TitleMOBILISE-D - Connecting digital mobility assessment to clinical outcomes for regulatory and clinical endorsement
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