Theoretical Study on Dihydrogen Bond Interaction Dominated Dodecaborate-Solvent Molecular Clusters

doi:10.6023/A25020041

Abstract

Dihydrogen bonds (DHB, X—H^δ⁺…H^δ—Y) have attracted significant attention due to their remarkable applications in molecular recognition, catalytic dehydrogenation, and drug design, etc. Although conventional hydrogen bonds (HBs) have been extensively and deeply studied, systematic research on these uncommon DHBs remains limited. Using high-level quantum chemical calculations and a dodecaborate-solvent molecular cluster model, this work systematically investigates the DHB interactions between dodecaborate anion ($\mathrm{B}_{12} \mathrm{H}_{12}^{2-}$) and ten different selected solvent molecules, including CH₃COOH, CH₃NO₂, CH₃CN, CH₃CHO, H₂O, CH₃OH, CH₃NH₂, CH₃F, CH₃CH₃, and CH₄. The results indicate that all solvent molecules (except CH₃F) form significant DHBs with $\mathrm{B}_{12} \mathrm{H}_{12}^{2-}$ anion. Among them, CH₃COOH exhibits the strongest binding energy (28.09 kcal•mol⁻¹), while CH₄ shows the weakest (3.58 kcal•mol⁻¹). Energy decomposition analysis (EDA) reveals that the contribution of electrostatic interactions in polar solvents significantly exceeds that in non-polar solvents, resulting in substantially higher binding energies for polar solvents. However, the dispersion and induction interactions play a dominant role in non-polar solvents. Further quantum theory of atoms in molecules (QTAIM) topological analysis shows that the electron density (ρ), Laplacian (∇²ρ), and kinetic energy density (G) at bond critical points (BCPs) agree well with the trend of binding energy, providing effective indicators for predicting the strength of DHB. Additionally, spectral simulation based on density of states (DOS) distribution reveals that different solvent molecules can effectively regulate the specific molecular orbitals of $\mathrm{B}_{12} \mathrm{H}_{12}^{2-}$ anion, thereby affecting its photoionization properties. This study comprehensively explores the interaction strength and quantum fundamental characteristics of boron-based DHBs, providing theoretical support for the expansion of applications dominated by DHB interactions in the future.

Key words: dihydrogen bond, dodecaborate anion, solvent-solute interaction, quantum chemical calculation, energy decomposition analysis

Cite this article

Xiaogai Peng, Zhubin Hu, Haitao Sun. Theoretical Study on Dihydrogen Bond Interaction Dominated Dodecaborate-Solvent Molecular Clusters[J]. Acta Chimica Sinica, 2025, 83(5): 510-517.

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Fig. & Tab. 7

Figure 1. The predicted most stable structures of dodecaborate-solvent ($\mathrm{B}_{12} \mathrm{H}_{12}^{2-}$•Solvent) molecular clusters

Figure 2. Calculated VDE values of various dodecaborate-solvent molecular clusters

团簇	实验值	计算值
团簇	实验值	PBE0	IP-EOM-DLPNO-CCSD
乙酸	—	1.88	1.90
硝基甲烷	—	1.74	1.75
乙腈	1.56^a	1.70	1.71
乙醛	—	1.63	1.65
水	1.46^b	1.63	1.62
甲醇	—	1.57	1.57
甲胺	—	1.49	1.52
氟代甲烷	—	1.53	1.53
乙烷	—	1.39	1.39
甲烷	—	1.35	1.36
裸硼烷	1.15^b	1.30	1.31

Table 1. Calculated VDE values of various dodecaborate-solvent molecular clusters (unit: eV)

Figure 3. (a) Total binding energies and energy decomposition (1 kcal/mol=4.184 kJ/mol); (b) ratio diagram of each interaction (green: electrostatic, yellow: dispersion, orange: induction) of the solute-solvent interaction in various dodecaborate-solvent molecular clusters

Figure 4. QTAIM analysis of different dodecaborate-solvent molecular clusters: (a) BCP points and topological path diagrams; (b) trends of six indicators and binding energies (all values have been averaged)

Figure 5. Electrostatic potential (ESP) graph of $\mathrm{B}_{12} \mathrm{H}_{12}^{2-}$•CH4 cluster (the maximum point in orange, and the minimum point in blue)

Figure 6. DOS diagram (black curve, full width at half maximum, FWHM=0.4 eV), energy level diagram (red line), and molecular orbitals of HOMO, HOMO-9, and HOMO-10 for the dodecaborate-solvent molecular clusters

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