Quantum chemical methods were employed to analyze the nature and the origin of the directionality of pnictogen (PnB), chalcogen (ChB), and halogen bonds (XB) in archetypal Fm Z⋅⋅⋅F- complexes (Z=Pn, Ch, X), using relativistic density functional theory (DFT) at ZORA-M06/QZ4P. Quantitative Kohn-Sham MO and energy decomposition analyses (EDA) show that all these intermolecular interactions have in common that covalence, that is, HOMO-LUMO interactions, provide a crucial contribution to the bond energy, besides electrostatic attraction. Strikingly, all these bonds are directional (i.e., F-Z⋅⋅⋅F- is approximately linear) despite, and not because of, the electrostatic interactions which, in fact, favor bending. This constitutes a breakdown of the σ-hole model. It was shown how the σ-hole model fails by neglecting both, the essential physics behind the electrostatic interaction and that behind the directionality of electron-rich intermolecular interactions. Our findings are general and extend to the neutral, weaker ClI⋅⋅⋅NH3 , HClTe⋅⋅⋅NH3 , and H2 ClSb⋅⋅⋅NH3 complexes.

Center for Basic and Applied Research University Hradec Kralove Hradec Kralove Czech Republic

Department of Chemical Sciences University of Johannesburg Auckland Park Johannesburg 2006 South Africa

Department of Chemistry Institute of Natural Sciences Federal University of Lavras CEP 37200 900 Lavras MG Brazil

Department of Theoretical Chemistry Amsterdam Institute for Molecular and Life Sciences Vrije Universiteit Amsterdam De Boelelaan 1083 1081 HV Amsterdam The Netherlands

Institute for Molecules and Materials Radboud University Nijmegen Heyendaalseweg 135 6525 AJ Nijmegen The Netherlands

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In Figure 6a, VS,max is ca. 1.8 Å from Cl along the molecular axis of FCl for isovalue of 0.001 a.u. In Figure 6b, VS,max is ca. 0.8 and 2.8 Å from Cl along the molecular axis of FCl for isovalues of 0.08 and 0.00001 a.u., respectively. For F−, the surface is ca. 0.5, 0.6, and 1.8 Å from the nucleus for isovalues of 0.4, 0.26, and 0.001 a.u., respectively.

Intramolecular Pnictogen Bonds as Key Determinants for NMR Quantum Computation Parameters

Crystal Clear: Decoding Isocyanide Intermolecular Interactions through Crystallography