Aromaticity and Through-Space Interaction between Aromatic Rings in [2.2]Paracyclophanes

Majerz, Irena; Dziembowska, Teresa

doi:10.1021/acs.jpca.6b05928

Cited by 22 publications

(25 citation statements)

References 47 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The presence of a C•••C bond path between the C atoms belonging to different rings in the [2.2]paracyclophane molecule and the charge density at the BCP ρ(r) > 0.0125 a.u. were taken as evidence for the presence of throughspace orbital interactions between the C atoms [21]. For [2.2] paracyclophane and [2.2]paracyclophane-7,9-diene and their derivatives investigated in this work, no bond path between the C•••C atoms in the different rings has been detected.…”

Section: Qtaim Analysis Of Substituted [22]paracyclophane [22]paramentioning

confidence: 90%

“…To characterize the conformation of the investigated paracyclophanes, we have used the following parameters: the distance between the benzene rings, the displacement of one aromatic ring relating to another (d in Scheme 1), and the twist of one ring in relation to another ring (the angle between the gray planes in Scheme 1) [21].…”

Section: Substituent Effect On the Geometry Aie And Se Energies Formentioning

confidence: 99%

“…The QTAIM analysis has been previously applied in the studies of [2.2]paracyclophane [10,11], [2.2]metacyclophane [9], and [n,n]paracyclophane complexes with cations [13]. In the previous paper [21], we applied the QTAIM analysis to investigate the through-space interactions in a series of unsubstituted and substituted [2.2]paracyclophanes. The presence of a C•••C bond path between the C atoms belonging to different rings in the [2.2]paracyclophane molecule and the charge density at the BCP ρ(r) > 0.0125 a.u.…”

Section: Qtaim Analysis Of Substituted [22]paracyclophane [22]paramentioning

confidence: 99%

“…An influence of the substitution on the structure and nature of π-π interaction in optimized molecules of cyclophanes was also investigated in a few papers [13,[18][19][20][21], but the problem is still far from being elucidated. This effect was more thoroughly studied for benzene dimers [15,[22][23][24][25][26].…”

Section: Introductionmentioning

confidence: 99%

“…In the previous paper [21], we investigated interactions between the aromatic rings of a series of [2,2]paracyclophanes using QTAIM and NCI analysis in both crystal structure and optimized [2.2]paracyclophanes with the parallel-displaced aromatic rings and additional bridges, and the existence of the through-space orbital interaction was stated. Contrary to expectation, no influence of the substituent effect on these interactions was observed.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Substituent effect on inter-ring interaction in paracyclophanes

Majerz

Dziembowska

2019

Mol Divers

Self Cite

View full text Add to dashboard Cite

The theoretical calculations, namely multipole-derived charge analysis, quantum theory of atom in molecules, and nonbonding interaction (NCI), were performed for [2.2]paracyclophanes, [2.2]paracyclophane-7,9-dienes, and [3.3]paracyclophanes optimized at B3LYP/6-311++G** level, including dispersion correction. The substituent effect of the electron donor N(Me) 2 and electron acceptor NO 2 group and the influence of the length of bridges joining the aromatic ring on aromatic ring interaction energy (AIE) and strain energy were discussed. The local and electrostatic character of the substituent effect in paracyclophanes was shown. The presence of the weak orbital through-space C•••C interaction between the [3.3]paracyclophane ring and weak CH•••O hydrogen bonds between the substituents in the different rings was shown.

show abstract

Section: Qtaim Analysis Of Substituted [22]paracyclophane [22]paramentioning

confidence: 90%

Section: Substituent Effect On the Geometry Aie And Se Energies Formentioning

confidence: 99%

Section: Qtaim Analysis Of Substituted [22]paracyclophane [22]paramentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Substituent effect on inter-ring interaction in paracyclophanes

Majerz

Dziembowska

2019

Mol Divers

Self Cite

View full text Add to dashboard Cite

show abstract

Molecular Insights into [2.2]Paracyclophane‐Based Functional Materials: Chemical Aspects Behind Functions

Hassan

2024

Adv Funct Materials

View full text Add to dashboard Cite

Many of the functions and features of practically useful materials are the province of molecular‐level chemistry and their modulation at different length‐scale. This report illustrates the molecular‐level chemistry behind functions and features of the [2.2]paracyclophane‐based materials with a particular focus on the most recent explorations on through‐space conjugated small‐molecule organic emitters, π‐stacked macrocyclic molecules and polymers, poly(p‐phenylenevinylene)s featuring well‐defined donor‐acceptors sequence control, and surface engineering of technologically‐relevant parylenes that finds broad applications across the field of chemical science and technology. This report largely deals with the potential and opportunities associated with molecular features and functions of planar chirality, conformational behaviors, strain‐induced non‐planarity of the aromatics, the profound impacts of through‐space conjugation and π‐electron interactions/delocalization on optoelectronic properties of the π‐conjugated organic emitters, polymers and extended structures consisting of cyclophanes. A special focus is put on the concept of supramolecular polymers using chemically‐programmed chiral cyclophanes via non‐covalent stacking and controlled conformational arrangements. Illustrating cyclophane as precursors/monomers and fabrication strategies for their incorporation in structurally‐controlled (poly(p‐xylylene)s formed via chemical vapor deposition polymerization and post‐deposition fabrication for interface engineering is described. Demonstrating a rather different approach of electronically‐dictated ring‐opening metathesis polymerization employing strained cyclophane‐diene precursors that generate conjugated poly(p‐phenylenevinylene)s with well‐defined (i.e., low dispersity) and donor‐acceptor sequence control is also discussed. This report will serve as an indispensable one‐stop reference for organic, and polymer chemists, as well as material scientists working with cyclophanes for research innovations.

show abstract

A Triply [5]Helicene‐Bridged (1,3,5)Cyclophane

et al. 2023

View full text Add to dashboard Cite

A rigid propeller‐shaped conjugated triple macrocycle consisting of two nearly perfectly stacked benzene rings and three linking [5]helicene moieties has been synthesized using a glyoxylic Perkin approach. Analysis of the electron delocalization in this atypical aromatic molecule revealed global aromaticity and a 78 π‐electron circuit along the edge of its triple loop, to the detriment of the two 6 π‐electron circuits in the two stacked benzene rings.

show abstract

Aromaticity and Through-Space Interaction between Aromatic Rings in [2.2]Paracyclophanes

Cited by 22 publications

References 47 publications

Substituent effect on inter-ring interaction in paracyclophanes

Substituent effect on inter-ring interaction in paracyclophanes

Molecular Insights into [2.2]Paracyclophane‐Based Functional Materials: Chemical Aspects Behind Functions

A Triply [5]Helicene‐Bridged (1,3,5)Cyclophane

Contact Info

Product

Resources

About