Supramolecular Assembly of Metal Complexes by (Aryl)I⋅⋅⋅d[Pt^II] Halogen Bonds

Abstract

The theoretical data for the half‐lantern complexes [{Pt(trueCN^ )(μ‐trueSN^ )}2] [1–3; trueCN^ is cyclometalated 2‐Ph‐benzothiazole; trueSN^ is 2‐SH‐pyridine (1), 2‐SH‐benzoxazole (2), 2‐SH‐tetrafluorobenzothiazole (3)] indicate that the Pt⋅⋅⋅Pt orbital interaction increases the nucleophilicity of the outer dz2 orbitals to provide assembly with electrophilic species. Complexes 1–3 were co‐crystallized with bifunctional halogen bonding (XB) donors to give adducts (1–3)2⋅(1,4‐diiodotetrafluorobenzene) and infinite polymeric [1⋅1,1′‐diiodoperfluorodiphenyl]n. X‐ray crystallography revealed that the supramolecular assembly is achieved through (Aryl)I⋅⋅⋅dz2 [PtII] XBs between iodine σ‐holes and lone pairs of the positively charged (PtII)2 centers acting as nucleophilic sites. The polymer includes a curved linear chain ⋅⋅⋅Pt2⋅⋅⋅I(areneF)I⋅⋅⋅Pt2⋅⋅⋅ involving XB between iodine atoms of the perfluoroarene linkers and (PtII)2 moieties. The 195Pt NMR, UV/Vis, and CV studies indicate that XB is preserved in CH(D)2Cl2 solutions.

(15‐crown‐5)BiI3 as a Building Block for Halogen Bonded Supramolecular Aggregates

“…We have also determined the optical band gaps of 1 and 2 (see Figure S7) as 2.34 and 2.22 eV, respectively, highlighting the small, but discernable difference between the two. A red‐shift in absorption bands has also been observed in other metal halide complexes upon interaction with halogen bond donors [35] . Similar band gaps have also been found in other neutral BiI 3 complexes, like [BiI 3 {(C 6 H 5 ) 3 PO} 2 ] 2 with a band gap of 2.37 eV [36] …”

“…A redshift in absorption bands has also been observed in other metal halide complexes upon interaction with halogen bond donors. [35] Similar band gaps have also been found in other neutral BiI 3 complexes, like [BiI 3 {(C 6 H 5 ) 3 PO} 2 ] 2 with a band gap of 2.37 eV. [36]…”

Intramolecular Spodium Bonds in Zn(II) Complexes: Insights from Theory and Experiment

“…In particular, the density and potential energy cubes used to generate the MEP surfaces and the wavefunction used as input to perform the QTAIM/NCI analyses were obtained using Gaussian-16. The PBE0-D3 level of theory has been recently used by us to analyze σ/π-hole interactions in the solid state [31][32][33][34][35][36][37][38]…”

Azine Steric Hindrances Switch Halogen Bonding to N‐Arylation upon Interplay with σ‐Hole Donating Haloarenenitriles

“…isosurface as an approximation to the van der Waals surface. This level of theory used in this work has been successfully used before to analyze similar interactions [97–99] . The NBO 3.0 analysis was carried out with the Gaussian‐16 program [89] at the same level of theory.…”