Mutual influence of tetrel and halogen bonds between XCN (X=Cl, Br) and 4-TF 3 -pyridine (T=C, Si, Ge)
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ORIGINAL PAPER
Mutual influence of tetrel and halogen bonds between XCN (X=Cl, Br) and 4-TF3-pyridine (T=C, Si, Ge) Qiang Zhao 1 Received: 6 September 2020 / Accepted: 28 October 2020 # Springer-Verlag GmbH Germany, part of Springer Nature 2020
Abstract Interplay between tetrel and halogen bonds in the XCN⋯4-TF3-pyridine⋯XCN (X=Cl, Br; T=C, Si, Ge) and 4-TF3pyridine⋯XCN⋯4-TF3-pyridine complexes was studied by using quantum chemical methods. The respective binary complexes XCN⋯4-TF3-pyridine and 4-TF3-pyridine⋯XCN have also been investigated. Mutual influence of both interactions has been analyzed in terms of the molecular electrostatic potential, binding distance, binding energy, electron density shift, and energy decomposition. Both the tetrel and halogen bonds have been strengthened in the ternary complexes. The cooperativity of the XCN⋯4-TF3-pyridine⋯XCN complex is more prominent than that of the 4-TF3-pyridine⋯XCN⋯4-TF3-pyridine complex. The variation of molecular electrostatic potentials in the binary complexes and the electron density shift of the complexes well explains this cooperative effect. Energy decomposition analysis revealed that the interactions are mainly dominated by electrostatic contribution; meanwhile, electrostatic contribution, induction, and dispersion enlarged in the ternary complexes. Keywords Tetrel bond . Halogen bond . Molecular electrostatic potential . Binding energy . Cooperativity
Introduction Noncovalent interactions play an important role in fields such as molecular recognition, chemical reactions, crystal engineering, and biological processes [1–3]. Hydrogen bond is the most extensively studied noncovalent interaction [4], and σ-hole interactions have attracted great attentions in recent years [5–7]. Clark et al. and Murray et al. [8, 9] proposed the concept of σhole, which represents a region of positive molecular electrostatic potential (MEP) on the outermost portion of an atomic surface. The σ-holes were identified on group IV, V, VI, and VII atoms, which correspond to tetrel bond [10], pnicogen bond [11], chalcogen bond [12], and halogen bond [13]. Halogen bond is a directional and electrostatically driven interaction, which has received considerable interest during the last two decades both experimentally and theoretically [6, 8, 9, 14–21]. The strength of halogen bond was mainly determined by electrostatics and polarization, and the importance of dispersion has been emphasized in recent years. Recently, tetrel * Qiang Zhao [email protected] 1
Department of Chemical Engineering, Zibo Vocational Institute, Zibo 255314, Shandong Province, People’s Republic of China
bond, which was proposed by Bauzá et al. [10], was identified in the Cambridge Structural Database (CSD). Tetrel bond has been applied in chemical reactions and crystal material [9, 22–31]. The strength of tetrel bond can compare with the halogen bond and other types of σ-hole interactions. Cooperativity is a common characteristic between two or more noncovalent interactions [32]. Interplay of these interaction
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