Dimers of borazine were studied using matrix isolation infrared spectroscopy and ab initio quantum chemical calculations. Computations were performed at the MP2 and M06-2X levels of theory using the 6-311++G(d,p) and aug-cc-pVDZ basis sets for the various homodimers. At both levels of theory, an aligned stacked structure was found to be the global minimum, which was nearly isoenergetic to a parallel displaced structure. A T-shaped structure, where the N-H of one borazine pointed towards the N of the second borazine, was found to be a local minimum. In addition to these structures, a dihydrogen bonded structure, where the hydrogen attached to the nitrogen of borazine interacted with the hydrogen attached to the boron atom of another borazine, was also indicated. Experimentally, we observed the T-shaped dimer and the dihydrogen bonded dimer. This is one of the rare examples of experimental evidence for a dihydrogen bond, in a system other than in a metal hydride. These results for the borazine dimer were clearly different from the benzene dimer where the parallel displaced structure was found to be the global minimum followed by the T-shaped structure at the MP2/aug-cc-pVDZ level of theory. AIM, EDA and NBO analyses were carried out for all the structures to explore the nature of interactions.

Hydrogen-bonded complexes of C2H2 and phenylacetylene (PhAc) were studied using matrix isolation infrared spectroscopy and quantum chemical computations. Both C2H2 and PhAc, being potential proton donors, the question arises as to which of the two species would be the proton donor in the PhAc-C2H2 complex; a question that this work primarily addresses. The molecular structures, vibrational frequencies, and interaction energies of the PhAc-C2H2 complexes were calculated at the M06-2X and MP2 levels of theory, employing both 6-311++G(d,p) and aug-cc-pVDZ basis sets. At the M06-2X/aug-cc-pVDZ level, two nearly isoenergetic complexes (BSSE corrected) were indicated to be the global minima; one a C-H···π complex, where C2H2 served as a proton donor to the phenyl π-system in PhAc, and the other a C-H···π complex, where C2H2 served as a proton donor to the acetylene π-system in PhAc. Of the two, only the second complex was identified in the matrix, evidenced by a characteristic large shift in the ≡C-H stretch of C2H2. Experiments were also performed using PhAc deuterated at the acetylene hydrogen (PhAcD) to study the isotopic effects on the vibrational spectra of complexes. The isotopic studies further confirmed the structure of the complex trapped in the matrix, thereby presenting unambiguous evidence that C2H2 served as the proton donor to the acetylene π-system of PhAc. The theory of atoms-in-molecules (AIM), energy decomposition (EDA), and natural bond orbital (NBO) analysis were performed to understand the nature of the interactions involved in the complexes.

Borazine is isoelectronic with benzene and is popularly referred to as inorganic benzene. The study of non-covalent interactions with borazine and comparison with its organic counterpart promises to show interesting similarities and differences. The motivation of the present study of the borazine-water interaction, for the first time, stems from such interesting possibilities. Hydrogen-bonded complexes of borazine and water were studied using matrix isolation infrared spectroscopy and quantum chemical calculations. Computations were performed at M06-2X and MP2 levels of theory using 6-311++G(d,p) and aug-cc-pVDZ basis sets. At both the levels of theory, the complex involving an N-H⋯O interaction, where the N-H of borazine serves as the proton donor to the oxygen of water was found to be the global minimum, in contrast to the benzene-water system, which showed an H-π interaction. The experimentally observed infrared spectra of the complexes corroborated well with our computations for the complex corresponding to the global minimum. In addition to the global minimum, our computations also located two local minima on the borazine-water potential energy surface. Of the two local minima, one corresponded to a structure where the water was the proton donor to the nitrogen of borazine, approaching the borazine ring from above the plane of the ring; a structure that resembled the global minimum in the benzene-water H-π complex. The second local minimum corresponded to an interaction of the oxygen of water with the boron of borazine, which can be termed as the boron bond. Clearly the borazine-water system presents a richer landscape than the benzene-water system.

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The heterodimers of borazine and benzene were studied using matrix isolation infrared spectroscopy and ab initio calculations, for an eventual comparison with the corresponding homodimers of the submolecules. The homo and hetero dimers are expected to show the stacked and T‐shaped structures as a general class of geometries; a study which promises to present an interesting comparison of the landscape of the homo and the heterodimers. Computations on the heterodimers were performed at the MP2 and M06‐2X levels of theory using aug‐cc‐pVDZ basis set. The heterodimer manifested both the T‐shaped and stacked structures, with the former being the global minimum. The T‐shaped structure itself showed two isoenergetic variations: one was the T‐NH structure, where the N−H of borazine pointed towards the center of the benzene ring and the second was the NH…C structure, where the N−H pointed towards a carbon atom of benzene; in short, the borazine formed the stem and the benzene formed cap of the T. We were able to discern both the T‐shaped structures in our matrix isolation experiments. A third geometry, the parallel displaced stacked structure, was indicated to be a local minimum, which however was not observed in our experiments. AIM, LMO‐EDA and NBO analysis was carried out to explore the nature of interactions in the various structures.

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