A Chiral Molecular Cage Comprising Diethynylallenes and N‐Heterotriangulenes for Enantioselective Recognition

Abstract

Chirality, a characteristic tool of molecular recognition in nature, is often a complement of redox active systems. Scientists, in their eagerness to mimic such sophistication, have designed numerous chiral systems based on molecular entities with cavities, such as macrocycles and cages. In an attempt to combine chirality and redox-active species, in this contribution we report the synthesis and detailed characterization of a chiral shapepersistent molecular cage based on the combination of enantiopure diethynylallenes and electron-rich bridged triarylamines, also known as N-heterotriangulenes. Its ability for chiral recognition in solution was revealed through UV/vis titrations with enantiopure helicenes.

Enantioselective Separation of Agricultural Fungicides Based on Chiral Hybrid Nanochannel Membranes

“…Fabrication of L/DAP[5]-Modified Binary Hybrid Nanochannel Membrane. The synthesis of L/D alanine functionalized pillar [5]arene (L/DAP [5]) is detailed in the Supporting Information (Scheme S1 and Figures S1−S9). By using the track-etching technique, the conical nanochannels were fabricated in a membrane made of PET (12 μm thickness, GSI, Germany).…”

“…1−3 The physiology of many chemical substances carries out the chemical processes in the phenomena of life in a highly asymmetric environment. 4,5 The generation of function is often attributed to the recognition and matching of chiral molecules. 6,7 With the development of research, people's understanding of life processes is deepening, and the study of chirality has aroused wide interest in the scientific community.…”

Dynamic Axial‐to‐Helical Communication Mechanism in Poly[(allenylethynylenephenylene)acetylene]s under External Stimuli

“…This chiral allene is a highly configurational and stable building block, which displayed outstanding chiroptical properties in the construction of allene-acetylenic oligomers, macrocycles, cages and supramolecular assemblies. [54][55][56][57][58][59][60] Based on this information, we became interested in studying the effect of transferring the molecular properties of allene-acetylenes to the corresponding helical polymers (Figure 2) by exploring a new mechanism of helical induction based on supramolecular interactions between allene and achiral molecules. So, we envisioned phenyl- acetylene monomers bearing (P)-and (M)-DEA-i.e., (P)-1 and (M)-1-(Figure 3a-b) as suitable building blocks.…”

“…For this reason, we focused our attention on 1,3‐diethynylallene [( P )‐ DEA , ( M ) ‐ DEA ] [53] (Figure 3a). This chiral allene is a highly configurational and stable building block, which displayed outstanding chiroptical properties in the construction of allene‐acetylenic oligomers, macrocycles, cages and supramolecular assemblies [54–60] …”

Pair of (Hg2II)3L2 Chiral Cages and Successive Transformation into (HgII)3L2 Chiral Cages: Chiral DOPA Recognition via Chiral Cages

“…Recently, research on desirable chiral coordination architectures has expanded into task-specific practical applications such as purification of chiral pharmaceuticals, recognition of chiral pollutants, preparation of bioactive foods, chiral catalysis, chiral isolation, and environmental problems. − Noteworthy modes of action of some coordination cages have been assigned, − and research on chiral cages that can selectively recognize useful chiral chemicals is a particularly hot research topic. − Both the confined space and the active site of chiral coordination cages are important factors for practical useful applications via specific weak interactions between the coordination cages and substrate molecules. Thus, various useful chiral coordination cages achieved via a stereogenic center, atropisomerism, or noncovalent weak interactions have been designed and constructed by various methodologies. − Numerous studies on the construction and applications of chiral coordination species have been devoted to the enantiorecognition of essential amino acids including chiral l - and d -proline − and to asymmetric catalysis reactions as well. − 3,4-Dihydroxyphenylalanine (DOPA) has been regarded as an important chiral molecule in the fields of medicine, biology, and marine adhesion. − l -DOPA, for instance, has been known to play a crucial role at the clinical level and in neurochemistry with respect to Parkinson′s disease, in contrast to its chiral isomer, inactive and toxic d -DOPA. , Thus, several chiral electroanalysis methods have been applied to distinguish DOPA enantiomers, including those entailing the application of self-assembled monolayers, molecularly imprinted sol–gel films, poly-lysine films, and chiral nanomaterials .…”