Dipole–dipole interactions in solution mixtures probed by two-dimensional synchronous spectroscopy based on orthogonal sample design scheme

• “Orthogonal Sample Design Scheme” was used to construct 2D spectroscopy.
• Dipole–dipole interactions of DMF/CH3COOC2H5, C60/CH3COOC2H5 in CCl4 were probed.
• Interactions were studied using FT-IR and combination of UV–Vis/FT-IR spectra.
• 2D synchronous spectrum can be used to characterize dipole–dipole interaction.

Two-dimensional (2D) synchronous spectroscopy together with a new approach called “Orthogonal Sample Design Scheme” was used to study the dipole–dipole interactions in two representative ternary chemical systems (N,N-dimethyllformamide (DMF)/CH3COOC2H5/CCl4 and C60/CH3COOC2H5/CCl4). For the first system, dipole–dipole interactions among carbonyl groups from DMF and CH3COOC2H5 are characterized by using the cross peak in 2D Fourier Transform Infrared Radiation (FT-IR) spectroscopy. For the second system, intermolecular interaction among π–π transition from C60 and vibration transition from the carbonyl band of ethyl acetate is probed by using 2D spectra. The experimental results demonstrate that “Orthogonal Sample Design Scheme” can effectively remove interfering part that is not relevant to intermolecular interaction. Additional procedures are carried out to preclude the possibilities of producing interfering cross peaks by other reasons, such as experimental errors. Dipole–dipole interactions that manifest in the form of deviation from the Beer–Lambert law generate distinct cross peaks visualized in the resultant 2D synchronous spectra of the two chemical systems. This work demonstrates that 2D synchronous spectra coupled with orthogonal sample design scheme provide us an applicable experimental approach to probing and characterizing dipole–dipole interactions in complex molecular systems.

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