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From Foldable Open Chains to Shape-Persistent Macrocycles: Synthesis, Impact on 2D Ordering, and Stimulated Self-Assembly.

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Title: From Foldable Open Chains to Shape-Persistent Macrocycles: Synthesis, Impact on 2D Ordering, and Stimulated Self-Assembly.
Authors: Soobin Kim1, Castillo, Henry D.2, Milim Lee1, Mortensen, Riley D.2, Tait, Steven L.2 tait@indiana.edu, Dongwhan Lee1 dongwhan@snu.ac.kr
Source: Journal of the American Chemical Society. 4/4/2018, Vol. 140 Issue 13, p4726-4735. 10p.
Subjects: Macrocyclic compounds, Molecular self-assembly, Intermolecular interactions, Conjugated oligomers, Ethylene glycols
Abstract: Small molecule self-assembly at surfaces offers an efficient route to highly ordered organic films that can be programmed for a variety of chemical and electronic applications. The success of these materials depends on the ability to program intermolecular interactions to guide precise structural ordering. Toward this objective, we have designed and synthesized a series of bis(triazolo)benzene-based π-conjugated molecules. Our synthesis exploits a last-stage C-C cross-coupling reaction to close up zigzag-shaped linear precursors to cyclized products, so that direct side-by-side comparisons can be made for their structure-dependent self-assembly behavior at surfaces and response to external stimuli. Indeed, scanning tunneling microscopy (STM) analysis revealed distinct differences as the conformational flexibility of the molecular backbone and the chemical structure of the peripheral groups are varied. Specifically, alkyl chains adsorb and form inter-digitated structures, whereas oligo ethylene glycol (OEG) chains remain desorbed and thus shift self-assembly to more densely packed π-conjugated cores. While the macrocycles self-assemble immediately and spontaneously, their linear precursors exhibit slower self-assembly kinetics, which could be attributed to the difference in the degree of conformational freedom. We also found that perturbation by the STM tip and the addition of co-solutes profoundly impacted the kinetics of self-assembly and surface patterning. This highly unusual behavior highlights the importance of noncovalent interactions that are inherently weak in solution but can be made strong for symmetric and conformationally restricted molecules confined within 2D surfaces. [ABSTRACT FROM AUTHOR]
Copyright of Journal of the American Chemical Society is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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DbLabel: Engineering Source
An: 128955172
AccessLevel: 6
PubType: Academic Journal
PubTypeId: academicJournal
PreciseRelevancyScore: 0
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  Data: From Foldable Open Chains to Shape-Persistent Macrocycles: Synthesis, Impact on 2D Ordering, and Stimulated Self-Assembly.
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  Data: <searchLink fieldCode="AR" term="%22Soobin+Kim%22">Soobin Kim</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Castillo%2C+Henry+D%2E%22">Castillo, Henry D.</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Milim+Lee%22">Milim Lee</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Mortensen%2C+Riley+D%2E%22">Mortensen, Riley D.</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Tait%2C+Steven+L%2E%22">Tait, Steven L.</searchLink><relatesTo>2</relatesTo><i> tait@indiana.edu</i><br /><searchLink fieldCode="AR" term="%22Dongwhan+Lee%22">Dongwhan Lee</searchLink><relatesTo>1</relatesTo><i> dongwhan@snu.ac.kr</i>
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  Data: <searchLink fieldCode="JN" term="%22Journal+of+the+American+Chemical+Society%22">Journal of the American Chemical Society</searchLink>. 4/4/2018, Vol. 140 Issue 13, p4726-4735. 10p.
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  Data: <searchLink fieldCode="DE" term="%22Macrocyclic+compounds%22">Macrocyclic compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Molecular+self-assembly%22">Molecular self-assembly</searchLink><br /><searchLink fieldCode="DE" term="%22Intermolecular+interactions%22">Intermolecular interactions</searchLink><br /><searchLink fieldCode="DE" term="%22Conjugated+oligomers%22">Conjugated oligomers</searchLink><br /><searchLink fieldCode="DE" term="%22Ethylene+glycols%22">Ethylene glycols</searchLink>
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  Label: Abstract
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  Data: Small molecule self-assembly at surfaces offers an efficient route to highly ordered organic films that can be programmed for a variety of chemical and electronic applications. The success of these materials depends on the ability to program intermolecular interactions to guide precise structural ordering. Toward this objective, we have designed and synthesized a series of bis(triazolo)benzene-based π-conjugated molecules. Our synthesis exploits a last-stage C-C cross-coupling reaction to close up zigzag-shaped linear precursors to cyclized products, so that direct side-by-side comparisons can be made for their structure-dependent self-assembly behavior at surfaces and response to external stimuli. Indeed, scanning tunneling microscopy (STM) analysis revealed distinct differences as the conformational flexibility of the molecular backbone and the chemical structure of the peripheral groups are varied. Specifically, alkyl chains adsorb and form inter-digitated structures, whereas oligo ethylene glycol (OEG) chains remain desorbed and thus shift self-assembly to more densely packed π-conjugated cores. While the macrocycles self-assemble immediately and spontaneously, their linear precursors exhibit slower self-assembly kinetics, which could be attributed to the difference in the degree of conformational freedom. We also found that perturbation by the STM tip and the addition of co-solutes profoundly impacted the kinetics of self-assembly and surface patterning. This highly unusual behavior highlights the importance of noncovalent interactions that are inherently weak in solution but can be made strong for symmetric and conformationally restricted molecules confined within 2D surfaces. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
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  Group: Ab
  Data: <i>Copyright of Journal of the American Chemical Society is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1021/jacs.8b01805
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      – Code: eng
        Text: English
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        PageCount: 10
        StartPage: 4726
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        Type: general
      – SubjectFull: Molecular self-assembly
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      – SubjectFull: Intermolecular interactions
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      – SubjectFull: Conjugated oligomers
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      – SubjectFull: Ethylene glycols
        Type: general
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      – TitleFull: From Foldable Open Chains to Shape-Persistent Macrocycles: Synthesis, Impact on 2D Ordering, and Stimulated Self-Assembly.
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            NameFull: Soobin Kim
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            NameFull: Castillo, Henry D.
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            NameFull: Milim Lee
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            NameFull: Mortensen, Riley D.
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            NameFull: Tait, Steven L.
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              Text: 4/4/2018
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              Y: 2018
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