In this study, we propose a new approach to generate two-dimension spectra to enhance the intensity of cross peaks relevant to intermolecular interaction. We investigate intermolecular interaction between two solutes (denoted as P and Q, where P has a characteristic peak at X) dissolved in the same solvent via the near diagonal cross peaks around the coordinate (X, X) in a two-dimensional (2D) asynchronous spectrum of generalized spectroscopy. Because of physical constrains in many cases, the variation ranges of the initial concentrations of P or Q must be kept very narrow, leading to very weak cross peak intensities. The weak cross peaks vulnerable to noise bring about difficulty in the investigation of subtle intermolecular interaction. Herein, we propose a new of way constructing a 2D asynchronous spectrum without the subtraction of the average spectrum often used as a reference spectrum. Mathematical analysis and computer simulation demonstrate that the near diagonal cross peaks around the coordinate (X, X) in the 2D asynchronous spectrum using the new approach possess two characteristics: (1) they can still reflect an intermolecular interaction reliably; 2) the absolute intensities of the cross peaks are significantly stronger than those generated by the conventional method. We incorporate the novel method with the DAOSD (double asynchronous orthogonal sample design scheme) approach and applied the modified DAOSD approach to study hydrogen bonding behavior in diethyl either/methanol/THF system. The new approach made the weak cross peaks, which are not observable in 2D asynchronous spectrum generated using conventional approach, become observable. The appearance of the cross peak demonstrate that When a small amount of THF is introduced into diethyl solution containing low amount of methanol, THF breaks the methanol-diethyl ether complex and forms methanol-THF complex via new hydrogen bond. This process takes place in spite of the fact that the content of diethyl ether is overwhelmingly larger than that of THF. The above result demonstrates that the new approach described in this article is applicable to enhance intensity of cross peaks in real chemical systems.

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A novel technique called AOSD@Job’s, combining asynchronous orthogonal sample design scheme (AOSD) with Job’s method, is proposed to estimate the stoichiometric ratio of two substances that form a supramolecular aggregate under intermolecular interactions. First, a mathematical analysis was performed along with the procedure of the AOSD@Job’s method. Then, the validity of the AOSD@Job’s method was manifested by computer simulation on two model systems. Finally, the AOSD@Job’s method was applied on two real chemical systems. The stoichiometric ratio between the coordination complex of Ni2+ and ethylenediaminetetraacetic acid disodium salt (EDTA) was estimated to be 1.0. Benzyl alcohol (BA) and β-cyclodextrin (β-CD) were determined to form a 1 : 1 host–guest complex. These values were consistent with the values reported in the literature. Compared with the traditional Job’s method, the AOSD@Job’s method has an evident advantage since it is still valid even if all the peaks of the supramolecular aggregate severely overlap with the peaks of the substances that form the aggregate.