An unlooked-for experimental observation that in
near-infrared
spectroscopy (NIR) the absorption peak of the second overtone of aniline adsorbed by 13X molecular sieve nearly disappeared led us investigate a fundamental question: the behavior of NIR when the outside space surrounding a molecule is too small to allow the molecule to vibrate freely. Through NIR of various organic compounds adsorbed by different porous inorganic materials like 13X molecular sieve, silica gel and active aluminium oxide, and NIR of supramolecular cyanuric acid-melamine, we can reasonably confirm a theoretical inference that in the micro-environment above, all intensities of NIR absorbance decrease, and the second overtone decreases more than the first overtone does. Furthermore, one distinct feature of NIR, higher sensitivity to the size of micro-environmental space as compared with mid-
infrared (MIR), and its potential application to the study of supramolecular structure are outlined by our experiments.