Abstract
Asymmetric tetrahedral carbon is the basic structural unit of many organic compounds in life and its molecular chirality plays a key role in regulating biological functions. Silica (SiO2) is highly earth abundant and its basic unit is also the tetrahedral form of SiO4. However, much less attention has been paid to the molecular-scale chirality of SiO2 frameworks with repeating SiO4 units because it is challenging to enantioselectively control the molecular structures of SiO2. Research into the chiral molecular structures of SiO2 deserves to be a significant topic for understanding widespread chiral phenomena and for exploring the chiral properties hidden in inorganic matter. This review highlights the asymmetric synthesis strategies that endow SiO2 with chirality transferred from asymmetric carbon at the molecular scale. The chirality transfer ability of SiO2 is also demonstrated for the construction of various inorganic and/or organic chiral materials with a wide range of applications in asymmetric synthesis, circularly polarized luminescence and Raman scattering-based chiral recognition.
Highlights
Chirality divides matter or light into a pair of non-superimposable enantiomeric forms with a mirror image relationship and occurs on a broad length scale from the molecular, to the nano/micro and even cosmic levels
It is known that proteins consisting of amino acid residues are chiral on all primary, secondary, tertiary and quaternary structural levels, among which the primary molecular chirality of amino acids plays a key role in chiral features and biological functions at higher levels[2]
With modern spectroscopic and electron microscopy techniques, the chiral features of such SiO2 materials have been demonstrated by: (1) helical outward shapes with pitches of over tens of nm, which are duplicated from the helical structures of organic templates in the sol-gel synthesis processes; and (2) inward chiral cavities, which are imprinted by chiral small molecules [Figure 1D]
Summary
Chirality divides matter or light into a pair of non-superimposable enantiomeric forms with a mirror image relationship and occurs on a broad length scale from the molecular, to the nano/micro and even cosmic levels. It has been confirmed that molecules or NPs, which are either physically attached to or chemically formed in chiral SiO2 nanomaterials, can become chiroptically active in CD spectra.
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