Synthesis of chiral inorganic or hybrid nanomaterials through sol-gel transcription of chiral organic templates has attracted a great deal of interest for more than a decade. However, the chiral nature of these inorganic matrices has never been directly observed. For the first time, we report a direct evaluation of chirality on noncrystalline silica chiral nanoribbons by vibrational circular dichroism (VCD) measurements. Strong Cotton effect around 1150-1000 cm from Si-O-Si asymmetric stretching vibration was observed. Surprisingly, calcination of these hybrid nanoribbons doubled the intensity of Cotton effects. On the basis of transmission electron microscopy observations, IR, VCD, NMR, and Raman spectroscopies, we demonstrate that the silica chirality originates from twisted siloxane network composed of chiral arrangement of the Si-O-Si bonds. Our findings clearly prove the presence of chiral organization of amorphous silica network, making them very promising chiral platforms for chiral recognition, optical applications, or asymmetric catalysis.

The synthesis of a cryptophane molecule bearing five methoxy substituents and an alkanethiol chain, 4, as well as its subsequent grafting onto a gold surface, is reported. Immobilization of cryptophane derivatives onto silica (SiO2/Au) surfaces was also performed by reacting a cryptophane molecule bearing one or six acid functions, 5 or 6, respectively, with an amino-terminated self-assembled monolayer (SAM). Polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS) was used to characterize the two types of cryptophane monolayers. Surface coverage of cryptophane monolayers was estimated by comparing the PM-IRRAS intensity of cryptophane bands with that calculated from the optical constants of pentamethoxy-cryptophane for a compact monolayer. A very efficient grafting of 4 onto a gold surface was found, with a surface coverage close to 100%. On the other hand, the reaction of mono-acid, 5, or hexa-acid, 6, cryptophanes with amino-terminated SAM was less efficient, since the surface coverage did not exceed 15%. Finally, a good surface coverage (75%) was also obtained by using a cysteamine coupling agent to modify 5 before its grafting onto a gold surface.