Morphological self-assembly of enantiopure allenes for upstanding chiral architectures at interfaces

Zhang, Yi‐Qi; Öner, Murat Anil; Lahoz, Inmaculada R.; Cirera, Borja; Palma, Carlos‐Andres; Castro‐Fernández, Silvia; Míguez-Lago, Sandra; Cid, Marı́a Magdalena; Barth, Johannes V.; Alonso‐Gómez, José Lorenzo; Klappenberger, Florian

doi:10.1039/c4cc06398h

Cited by 13 publications

(15 citation statements)

References 37 publications

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“…Structures of (A) ( M , M )‐ CF ‐ 1 and (B) ( M )‐ CF ‐ 2 previously studied for surface functionalization…”

Section: Introductionsupporting

confidence: 86%

“…To this end, we employed chiral framework (CF) CF‐1 bearing allenes on Ag (111) under vacuum conditions (Figure A). While the molecular chirality was transferred to 2D nanostructures by the formation of up‐standing chiral architectures (UCAs), the poor stability of these first examples hindered the exploration of chiroptical responses at room temperature . To tackle this challenge, we undertook the strategy of self‐assembled monolayers (SAMs) and synthesized both enantiomers of thioacetate‐derivatized CF‐2 for the functionalization of Au surfaces (Figure B).…”

Section: Introductionmentioning

confidence: 99%

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Design and synthesis of chiral spirobifluorenes

2020

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Chiroptical spectroscopic methods serve as a practical tool for the structural characterization of chiral systems based on the interaction with polarized light. The higher sensitivity of these methods, compared with their achiral counterparts, not only enables the determination of absolute configuration and conformational preferences, but also supramolecular interactions may be monitored. In order to expand the applicability of chiroptical systems, the development of functional materials exhibiting intense chiroptical responses is essential. As a proof of principle, we previously constructed chiroptical interfaces via thioacetate‐derivatized allenes. Because of the photoisomerization issues associated with allenes, we have recently proposed their replacement by spirobifluorenes to achieve robust chiroptical systems. Thus, we hereby present the design and synthesis of chiral spirobifluorenes bearing thioacetates suitable for suface functionalization.

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“…Structures of (A) ( M , M )‐ CF ‐ 1 and (B) ( M )‐ CF ‐ 2 previously studied for surface functionalization…”

Section: Introductionsupporting

confidence: 86%

Section: Introductionmentioning

confidence: 99%

Design and synthesis of chiral spirobifluorenes

2020

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“…25 b: Synthesis and enantiomeric resolution of (±)-CF-2. Reagents and conditions: i) mesyl chloride, Et3N, CH2Cl2, 0 °C to 25 °C, 22 h; ii) CH3COSK, DMF, 0 °C to 25 °C, 4 h, 80%; iii) Et3N, [Pd(PPh3)4], THF, 65 °C, 72 h, 46%; iv) Chiralpak® IA, 96:4 n-Hex/i-PrOH, 4.0 mL min -1 .…”

Section: Resultsmentioning

confidence: 99%

“…Under such ideal conditions, we demonstrated the formation of upstanding chiral architectures (UCAs), in which the single chiral molecules are arranged perpendicular to the underlying substrate as 2D nanostructures with possibilities for post-synthetic modification. 25 However, the weak moleculesubstrate interactions hindered the exploration of the chiroptical responses of the formed chiral surfaces at room temperature (RT). Herein, we present the design and synthesis of enantiopure (P)-CF-2 and (M)-CF-2 (Scheme 1) and their use for surface functionalization.…”

Section: Introductionmentioning

confidence: 99%

Device-Compatible Chiroptical Surfaces through Self-Assembly of Enantiopure Allenes

Ozcelik¹,

Pereira-Cameselle²,

Weber

et al. 2018

Langmuir

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Chiroptical methods have been proven to be superior compared to their achiral counterparts for the structural elucidation of many compounds. In order to expand the use of chiroptical systems to everyday applications, the development of functional materials exhibiting intense chiroptical responses is essential. Particularly, tailored and robust interfaces compatible with standard device operation conditions are required. Herein, we present the design and synthesis of chiral allenes and their use for the functionalization of gold surfaces. The self-assembly results in a monolayer-thin room-temperature-stable upstanding chiral architecture as ascertained by ellipsometry, X-ray photoelectron spectroscopy, and near-edge X-ray absorption-fine-structure. Moreover, these nanostructures anchored to device-compatible substrates features intense chiroptical second harmonic generation. Both straight-forward preparation of the device-compatible interfaces along with their chiroptical nature provide major prospects for everyday applications.

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“…As a step further towards chiroptical devices, we have incorporated functional groups leading to the recognition of halogenated compounds with pyridoallenophanes, and to the chiroptical detection of sandwich organometallic compounds with covalent organic molecular cages . Additionally, with the aim of expanding the applicability of chiroptical responses, we succeeded in surface functionalization with chiral allenes as up‐standing chiral architectures . However, photoisomerization of the allene moieties when directly conjugated with electron‐rich functional groups limits the scope of this chiral building block for applications.…”

Section: Methodsmentioning

confidence: 99%

Diverse Chiral Scaffolds from Diethynylspiranes: All‐Carbon Double Helices and Flexible Shape‐Persistent Macrocycles

Castro‐Fernández

Ren

García

et al. 2017

Chemistry A European J

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State-of-the-art chiroptical spectroscopies are valuable tools for structural elucidation. However, the potential of these spectroscopies for everyday applications has not been exploited to date partially due to the lack of sufficiently stable and efficient chiroptical systems. To this end, the development of suitable chiroptical structures is essential. Herein, we present the synthesis of spiro-compounds (P )-1 and (P )-2 as well as (M )-1 and (M )-2 exhibiting remarkable chiroptical responses. Theoretical simulations show that (P )-1, constituted by two (P)-configured spiranic chiral axes, presents an all-carbon double helix structure with (M)-helicity. On the other hand, molecular dynamic simulations reveal (P )-2 to have a single path for geometry-modification along its flat conformational space, certifying it as a chiral flexible shape-persistent macrocycle. Geometric quantification of chirality has been used to compare the spiranic derivatives presented herein.

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Morphological self-assembly of enantiopure allenes for upstanding chiral architectures at interfaces

Cited by 13 publications

References 37 publications

Design and synthesis of chiral spirobifluorenes

Design and synthesis of chiral spirobifluorenes

Device-Compatible Chiroptical Surfaces through Self-Assembly of Enantiopure Allenes

Diverse Chiral Scaffolds from Diethynylspiranes: All‐Carbon Double Helices and Flexible Shape‐Persistent Macrocycles

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