Diiodomethane as a halogen bond donor toward metal-bound halides

Abstract

A 1, 3,5,7,3,6, chloride platinumIJII) complex (1) was obtained via the metal-mediated double coupling of 2,3-diphenylmaleimidine with both nitrile ligands in trans-Compound 1 was then co-crystallized with diiodomethane forming solvate 1·½CH 2 I 2 . The XRD experiment reveals that this solvate displays the halogen bonds H 2 C(I)-I⋯Cl-Pt and hydrogen bonds I 2 C(H)-H⋯Cl-Pt, which join two complex and one CH 2 I 2 molecules in a heterotrimeric supramolecular cluster. Inspection of the CCDC database reveals only one example of the halogen bond H 2 C(I)-I⋯I-Pt between the CH 2 I 2 molecule and metal-coordinated halide in the structure of VEMWOA. In VEMWOA, CH 2 I 2 serves solely as a halogen bond donor with no hydrogen bond contribution. Results of the Hirshfeld surface analysis and DFT calculations (M06/DZP-DKH level of theory) followed by topological analysis of the electron density distribution within the formalism of Bader's theory (QTAIM method) for both 1·½CH 2 I 2 and VEMWOA confirmed the formation of these weak interactions. The evaluated energies of halogen bonds involving CH 2 I 2 are in the 2.2-2.8 kcal mol −1 range.

Revealing Factors Influencing the Fluorine‐Centered Non‐Covalent Interactions in Some Fluorine‐Substituted Molecular Complexes: Insights from First‐Principles Studies

“…As illustrated in Figures 4 and 5, the interactions between the negative sites on the fluorine atoms are highly directional in some complexes, forming a type‐II halogen bond pattern (to avoid confusion, we note that a halogen bond pattern does not imply type‐II halogen bond by itself) ,. For instance, the ∠C−F⋅⋅⋅F are 171.6 and 175.7° for the geometries illustrated in b) and c) of Figure , respectively.…”

Polymeric Lead(II) Iodoacetate: Pb···I and I···I Non‐Covalent Interactions in the Solid State

“…In order to investigate the nature of the Pb ··· I and I ··· I contacts in 1 , DFT calculations and topological analysis of the electron density distribution within the framework of Bader's theory (QTAIM method) were performed for oligomeric cluster of 1 (see Supporting Information). Previously, this approach was used by us for upon studies of various non‐covalent interactions in solid state , . Results are summarized in Table ; the Poincare–Hopf relationship was satisfied, and all critical points were found.…”

“…Apart from fundamental interest, this special type of non‐covalent interactions provides attractive tools for design of functional materials and sensor systems . Currently, there exist several classes of organic “building blocks” which are especially widely applied when aiming formation of XB, in particular, iodoarenes, halogenated alkanes, polyhalides,, halogenated pyridines, etc. Halogenated carboxylic acids (both aromatic and aliphatic) are rarely utilized as XB building blocks, in particular with heavier halides where the formation of halogen bonds can be expected.…”

Chlorobismuthates Trapping Dibromine: Formation of Two‐Dimensional Supramolecular Polyhalide Networks with Br2 Linkers

“…To investigate the nature of Br ··· Cl interactions and quantify their energies, we carried out DFT calculations and performed topological analysis of the electron density distribution within the formalism of Bader's theory (QTAIM method) for the fragments of 1 – 3 (atomic coordinates obtained by XRD were used). Previously, this approach has been successfully used by us in studies of different non‐covalent interactions (e.g., hydrogen, halogen, and chalcogen bonding, metallophilic interactions, stacking), and properties of coordination bonds in various transition metal complexes . The results are summarized in Table ; the contour line diagram of the Laplacian distribution ∇ 2 ϱ ( r ), bond paths, and selected zero‐flux surfaces for 1 are shown in Figure .…”