Solid-State (19)F NMR Chemical Shift in Square-Planar Nickel–Fluoride Complexes Linked by Halogen Bonds

[Image: see text] The halogen bond (XB) is a highly directional class of noncovalent interactions widely explored by experimental and computational studies. However, the NMR signature of the XB has attracted limited attention. The prediction and analysis of the solid-state NMR (SSNMR) chemical shift tensor provide useful strategies to better understand XB interactions. In this work, we employ a computational protocol for modeling and analyzing the (19)F SSNMR chemical shifts previously measured in a family of square-planar trans Ni(II)-L(2)-iodoaryl-fluoride (L = PEt(3)) complexes capable of forming self-complementary networks held by a NiF···I(C) halogen bond [ V. Thangavadivale; Chem. Sci.2018, 9, 3767−378129780509]. To understand how the (19)F NMR resonances of the nickel-bonded fluoride are affected by the XB, we investigate the origin of the shielding in trans-[NiF(2,3,5,6-C(6)F(4)I)(PEt(3))(2)], trans-[NiF(2,3,4,5-C(6)F(4)I)(PEt(3))(2)], and trans-[NiF(C(6)F(5))(PEt(3))(2)] in the solid state, where a XB is present in the two former systems but not in the last. We perform the (19)F NMR chemical shift calculations both in periodic and molecular models. The results show that the crystal packing has little influence on the NMR signatures of the XB, and the NMR can be modeled successfully with a pair of molecules interacting via the XB. Thus, the observed difference in chemical shift between solid-state and solution NMR can be essentially attributed to the XB interaction. The very high shielding of the fluoride and its driving contributor, the most shielded component of the chemical shift tensor, are well reproduced at the 2c-ZORA level. Analysis of the factors controlling the shielding shows how the highest occupied Ni/F orbitals shield the fluoride in the directions perpendicular to the Ni–F bond and specifically perpendicular to the coordination plane. This shielding arises from the magnetic coupling of the Ni(3d)/F(2p lone pair) orbitals with the vacant σ(Ni–F)(*) orbital, thereby rationalizing the very highly upfield (shielded) resonance of the component (δ(33)) along this direction. We show that these features are characteristic of square-planar nickel–fluoride complexes. The deshielding of the fluoride in the halogen-bonded systems is attributed to an increase in the energy gap between the occupied and vacant orbitals that are mostly responsible for the paramagnetic terms, notably along the most shielded direction.