On the formation of sandwich and multidecker complexes via π⋯π interaction: a DFT study

Abstract

Sandwich and multidecker complexes via organic π–inorganic π interaction.

Nonclassical B‐Hb⋯π interaction in diborane⋯localized‐π sandwiches: A DFT‐D3 study

“…For example, ΔE av values for O 2 ‐B 2 H 6 ‐O 2 , C 2 H 4 ‐B 2 H 6 ‐C 2 H 4 , and C 2 H 2 ‐B 2 H 6 ‐C 2 H 2 sandwiches are 0.45, 1.0, and 0.95 kcal mol −1 , respectively while for B 2 H 6 ‐O 2 , B 2 H 6 ‐C 2 H 4 , and B 2 H 6 ‐C 2 H 2 half sandwiches the estimated ΔE values are 0.4, 0.9, and 0.9 kcal mol −1 , respectively. Literatures on sandwiches involving B‐H b ⋯π and π⋯π interactions (arene) have predicted lower ΔE av as compared to their corresponding ΔE values for half sandwiches . The strength of B‐H b ⋯π interaction with localized π‐systems are significantly smaller than that with delocalized π‐systems.…”

“…It has already been reported that ΔE values for sandwiches are higher as compared to half sandwiches formed via B‐H b ⋯π and π⋯π interactions . Stability of the sandwiches can be better expressed from the average stabilization energy (ΔE av ) that is defined as the total stabilization energy divided by total number of B‐H b ⋯π interactions in the complex.…”

“…However, studies on B‐H b ⋯π interaction involving localized π‐electrons have received little attention. Moreover, the strength of B‐H b ⋯π interaction (in sandwiches) with delocalized π‐electrons has been reported to be comparable to that of the interaction between localized‐π and delocalized‐π electrons . This stimulated the study of the interaction between H b and localized‐π electrons.…”

DFT Study on the Formation of Homo and Hetero dimers of BN‐doped Tetracyclic fused Aromatics via π⋯π Stacking

“…Although B3LYP‐D3(BJ)/cc‐pVTZ level of theory produced relatively accurate results for the model systems, considering the size of the complexes instead of re‐optimization, single point calculations are performed on the optimized geometries at B3LYP‐D3(BJ)/cc‐pVTZ level of theory. Recent literatures also validated the suitability of this protocol for scrutinizing the role of basis sets . Apart from this, to check the consistency of the results, geometries are re‐optimized at M06‐2X/6‐31++G(d,p) and ωB97X‐D/6‐31++G(d,p) level of theories.…”

“…Recent literatures also validated the suitability of this protocol for scrutinizing the role of basis sets. [26] Apart from this, to check the consistency of the results, geometries are re-optimized at M06-2X/6-31 + + G(d,p) and ωB97X-D/6-31 + + G(d,p) level of theories. This would enable to gauze the role of functional in predicting the stability of the complexes.…”