Halogen Bonding with Phosphine: Evidence for Mulliken Inner Complexes and the Importance of Relaxation Energy

Abstract

Intermolecular halogen bonding in complexes of phosphine and dihalogens has been theoretically investigated using explicitly correlated coupled cluster methods and sym-

Methylammonium Lead Trihalide Perovskite Solar Cell Semiconductors Are Not Organometallic: A Perspective

“…The amount of this charge transfer is > 0.14 e (computed with M06‐2X/ADZP), much larger than typical value (≪ 0.1 e ) generally observed for weak to medium and strong intermolecular interactions . For this reason, one might wish to classify the MAPbY 3 complexes as Mulliken inner type …”

A Computational Study of Chalcogen‐containing H2X…YF and (CH3)2X…YF (X=O, S, Se; Y=F, Cl, H) and Pnicogen‐containing H3X′…YF and (CH3)3X′…YF (X′=N, P, As) Complexes

“…[35] Noncovalent interactions involving pnicogen atoms have been widely studied. [43][44][45][46][47] Some interesting points emerged from a recent theoretical study of halogen bonding in complexes of phosphine H 3 P. [48] It was found that the relative energetic stabilities of these H 3 P complexes with various YZ (Y,Z = halogen) bases, especially in H 3 P…ClF, depended on how the interaction energies were defined and computed. [36][37][38][39][40][41][42] The effect of other types of intermolecular interactions in pnicogen-bonded complexes has also been studied.…”

“…Factors influencing the structure, energy and properties of pnicogen-bonded complexes, including the nature of the pnicogen atom and substituent effects on the Lewis acid and Lewis base molecular subunits of these complexes, have been obtained from theoretical studies. [48] In the present study, we consider two measures of the interaction energy for our model complexes, one which takes into account the deformation energy (i. e. the energy required to deform the monomer subunits from their equilibrium geometries to the geometries they adopt in the optimized complex) and one which does not. [43][44][45][46][47] Some interesting points emerged from a recent theoretical study of halogen bonding in complexes of phosphine H 3 P. [48] It was found that the relative energetic stabilities of these H 3 P complexes with various YZ (Y,Z = halogen) bases, especially in H 3 P…ClF, depended on how the interaction energies were defined and computed.…”

“…[36][37][38][39][40][41][42] The effect of other types of intermolecular interactions in pnicogen-bonded complexes has also been studied. [28,48] In the present study, we find that the difference in electronegativity of the X and Y atoms of the model H 2 X…YF and (CH 3 ) 2 X…YF (X=O, S, Se; Y=F, Cl, H) and H 3 X'…YF and (CH 3 ) 3 X'…YF (X'=N, P, As) complexes is useful in rationalizing the energetic trends obtained, especially the anomalous stability of some complexes of F 2 . [48] In the present study, we consider two measures of the interaction energy for our model complexes, one which takes into account the deformation energy (i. e. the energy required to deform the monomer subunits from their equilibrium geometries to the geometries they adopt in the optimized complex) and one which does not.…”

Regular/abnormal variation in the strength and nature of the halogen bond between H2Te and the dihalogens: Prominent effect of methyl substituents

“…Thus, the charge transfer interaction is more important in the Te···X halogen bond. It should be mentioned that halogen‐bonded complexes have been classified as charge‐transfer complexes in previous studies . The large charge transfer in the Te complex suggests that Te is conducive for efficient electrical and atomic transport along the weak interaction path .…”