Homoconjugation vs. Exciton Coupling in Chiral α,β-Unsaturated Bicyclo[3.3.1]nonane Dinitrile and Carboxylic Acids

Bagdžiūnas, Gintautas; Butkus, Eugenijus; Stončius, Sigitas

doi:10.3390/molecules19079893

Cited by 3 publications

(3 citation statements)

References 38 publications

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“…In addition to providing a modern theoretical framework to the coupled oscillator theory, MO analysis based on QM calculations has a practical application concerning requisite (c) in our lettered list. Examination of MOs, NTOs, and transition densities is in fact helpful to distinguish between truly exciton‐coupled chromophores and cases where the two putative chromophores are in fact conjugated, so ECM cannot be applied (see Examples 14 and 15 above and other literature reports) 132,133 …”

Section: Quantitative Predictions Of Exciton‐coupled Ecd Spectramentioning

confidence: 99%

“…Examination of MOs, NTOs, and transition densities is in fact helpful to distinguish between truly exciton‐coupled chromophores and cases where the two putative chromophores are in fact conjugated, so ECM cannot be applied (see Examples 14 and 15 above and other literature reports). 132 , 133 …”

Section: Quantitative Predictions Of Exciton‐coupled Ecd Spectramentioning

confidence: 99%

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ECD exciton chirality method today: a modern tool for determining absolute configurations

Pescitelli

2021

Chirality

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The application of the exciton chirality method (ECM) to interpret electronic circular dichroism (ECD) spectra is a well-established and still popular approach to assign the absolute configuration (AC) of natural products, chiral organic compounds, and organometallic species. The method applies to compounds containing at least two chromophores with electric dipole allowed transitions (e.g., π-π* transitions). The exciton chirality rule correlates the sign of an exciton couplet (two ECD bands with opposite sign and similar intensity) with the overall molecular stereochemistry, including the AC. A correct application of the ECM requires three main prerequisites: (a) the knowledge of the molecular conformation, (b) the knowledge of the directions of the electric transition moments (TDMs), and (c) the assumption that the exciton coupling mechanism must be the major source of the observed ECD signals. All these prerequisites can be easily verified by means of quantum-mechanical (QM) calculations. In the present review, we shortly introduce the general principles that underpin the use of the ECM for configurational assignments and survey its applications, both classic ones and some reported in the recent literature. Based on these examples, we will stress the advantages of the ECM but also the key requisites for its correct application. Additionally, we will discuss the dependence of the couplet sign on geometrical parameters (angles α,β,γ between TDMs), which can be helpful for discerning the sign of exciton chirality in ambiguous situations. Finally, we will present a molecular orbital (MO) description of the exciton coupling phenomenon.

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Section: Quantitative Predictions Of Exciton‐coupled Ecd Spectramentioning

confidence: 99%

Section: Quantitative Predictions Of Exciton‐coupled Ecd Spectramentioning

confidence: 99%

ECD exciton chirality method today: a modern tool for determining absolute configurations

Pescitelli

2021

Chirality

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“…Supramolecular synthons based on the chiral rigid bicyclo[3.3.1]nonane core as the configurationally stable Tröger’s base analogue have served as excellent model systems for supramolecular applications. − Moreover, the chiral bicyclo[3.3.1]nonane framework is often used for fundamental studies on chiroptical properties of polyfunctional molecules such as α,β-unsaturated dinitrile and carboxylic acids, dibenzoyl esters, and enones , and other molecular systems …”

Section: Introductionmentioning

confidence: 99%

Hierarchical Assembly toward Nanoparticles of a Chiral Palladium Supramolecular Complex Based on Bicyclo[3.3.1]nonane Framework

2019

Self Cite

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The cyclic supramolecular coordination constructs were synthesized via metal-directed self-assembly from cis-protected Pd(II) precursor and chiral and racemic C 2 symmetric V-shaped bicyclo[3.3.1]nonane-based ligands incorporating pyridyl groups. In the complexes, these ligands act as bridges to connect together metal centers resulting in dinuclear and tetranuclear assemblies capable of further hierarchical aggregation on surfaces as well as in solution. Supramolecular structures obtained were characterized by mass spectrometry and NMR spectroscopy. Chiroptical properties of the ligand and the corresponding complex have also been analyzed. Moreover, the atomic force microscopy and dynamic light scattering experiments revealed a formation of stable nanoparticles from these complexes in the solution and the solid state.

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Substituent and intramolecular hydrogen-bond effect on the fluorescent emission of two easy-synthesizable fused rigid bicyclic octadiene derivatives

Muñoz

Cumsille

Günther

et al. 2017

Journal of Molecular Structure

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Homoconjugation vs. Exciton Coupling in Chiral α,β-Unsaturated Bicyclo[3.3.1]nonane Dinitrile and Carboxylic Acids

Cited by 3 publications

References 38 publications

ECD exciton chirality method today: a modern tool for determining absolute configurations

ECD exciton chirality method today: a modern tool for determining absolute configurations

Hierarchical Assembly toward Nanoparticles of a Chiral Palladium Supramolecular Complex Based on Bicyclo[3.3.1]nonane Framework

Substituent and intramolecular hydrogen-bond effect on the fluorescent emission of two easy-synthesizable fused rigid bicyclic octadiene derivatives

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