Five-Fold-Symmetric Macrocyclic Aromatic Pentamers: High-Affinity Cation Recognition, Ion-Pair-Induced Columnar Stacking, and Nanofibrillation

Ren, Changliang; Maurizot, Victor; Zhao, Huaiqing; Shen, Jie; Zhou, Feng; Ong, Wei Qiang; Du, Zhiyun; Zhang, Kun; Su, Haibin; Zeng, Huaqiang

doi:10.1021/ja206457b

Cited by 77 publications

(53 citation statements)

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“…The one-pot reaction following the chain-growth mechanism of the difunctional monomers 246 allowed the preparation of the macrocyclic products 245b in 10−25% yield ( Figure 72). 271,272 Despite that usually fluorine acts as a poor hydrogen bond acceptor, Zeng and co-workers have described the preparation of some cyclic oligoamides 248 using C−F···H−N hydrogen bonds, much weaker than the CO···H−N hydrogen bonds, to appropriately preorganize the open-chain immediate precursor 247. Macrocyclization yields obtained were in the 11−22% range ( Figure 73).…”

Section: Conformational Preorganizationmentioning

confidence: 99%

Macrocyclization Reactions: The Importance of Conformational, Configurational, and Template-Induced Preorganization

et al. 2015

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Section: Conformational Preorganizationmentioning

confidence: 99%

Macrocyclization Reactions: The Importance of Conformational, Configurational, and Template-Induced Preorganization

et al. 2015

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“…4,33−38 In these systems, the impact of the counteranion's form factor (size, shape) and its electronics on the material shifts from the anion to the complex. 28,33 This cation−anion−receptor approach has the potential to leverage the already extensive varieties of anion receptors 39,40 to engineer optical properties by simply mixing the building blocks together (Figure 1). However, examples of these materials are still rare; for example, they have been restricted to halide salts.…”

Section: ■ Introductionmentioning

confidence: 99%

Ion-Pair Oligomerization of Chromogenic Triangulenium Cations with Cyanostar-Modified Anions That Controls Emission in Hierarchical Materials

et al. 2017

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The hierarchical assembly of colored cationic molecules with receptor-modified counteranions can be used to control optical properties in materials. However, our knowledge of when the optical properties emerge in the hierarchical organization and the variety of cation-anion salts that are available to create these materials is limited. In this work, we extend the salts from small halides to large inorganic anions and determine how the structure coevolves with the emission properties using solution assemblies. We study the chromogenic trioxatriangulenium (TOTA) cation and its coassembly with cyanostar (CS) macrocycles selected to modify tetrafluoroborate (BF) counteranions through formation of 2:1 sandwich complexes. In the solid state, the TOTA cation stacks in an alternating manner with the sandwich complexes producing new red-shifted emission and absorption bands. Critical to assigning the structural origin of the new optical features across the four levels of organization (1° → 4°) is the selection of specific solvents to produce and characterize different assemblies present in the hierarchical structure. A key species is the electrostatically stabilized ion pair between the TOTA cation and sandwich complex. The red-shifted features only emerge when the ion pairs oligomerize together into larger (TOTA·[CSBF]) assemblies. New electronic states emerge as a result of multiple copies of the TOTA making π-contact with cyanostar-anion complexes. Our findings and the ease with which the materials can be prepared as crystals and films by mixing the salt with a receptor provide a strong platform for the de novo design of new optical materials.

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“…32 The synthesis of macrocyclic structures from folded oligomers 23,33,34 that function as receptors 23,[35][36][37][38][39][40] has stemmed from these endeavors.…”

Section: Scheme 1 Selected Conformational Preference Of Amide Bonds Imentioning

confidence: 99%

Synthesis of Oligobenzamide α-Helix Mimetics

Burslem

Wilson

2013

Synlett

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The development of inhibitors of protein-protein interactions (PPIs) represents a major challenge in chemical biology. α-Helix-mediated PPIs represent a subclass that might be amenable to inhibition using scaffolds that reproduce the spatial projection of recognition groups produced by the helix; these ligands are termed proteomimetics. Such a generic scaffold approach requires robust chemistry that can be used to synthesize reasonably large libraries of compounds. Foldamers are defined as oligomers that adopt welldefined folded structures. An ultimate goal of research in this area is to be able to reproduce and surpass the functionality of natural biopolymers; again a key enabling technology in this pursuit is robust synthetic methodology with a broad substrate scope. When we started our research program in this area seven years ago, we were drawn to aromatic oligoamide foldamers as potential proteomimetic scaffolds; however, in contrast to more widely studied β-peptideand peptoid-based foldamers, the synthesis of aromatic oligoamides was less well developed in terms of monomer diversity and amenability to library synthesis. This account describes our efforts and, more generally, the development of methodologies for the synthesis of aromatic oligoamides during this period.

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Five-Fold-Symmetric Macrocyclic Aromatic Pentamers: High-Affinity Cation Recognition, Ion-Pair-Induced Columnar Stacking, and Nanofibrillation

Cited by 77 publications

References 53 publications

Macrocyclization Reactions: The Importance of Conformational, Configurational, and Template-Induced Preorganization

Macrocyclization Reactions: The Importance of Conformational, Configurational, and Template-Induced Preorganization

Ion-Pair Oligomerization of Chromogenic Triangulenium Cations with Cyanostar-Modified Anions That Controls Emission in Hierarchical Materials

Synthesis of Oligobenzamide α-Helix Mimetics

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