Effect of through-bond interaction on conformation and structure of some N-arylpiperidone and N-aryltropanone derivatives. 2

Krijnen, Bert; Beverloo, H. B.; Verhoeven, J. W.; Reiss, C. A.; Goubitz, K.; Heijdenrijk, D.

doi:10.1021/ja00194a044

Cited by 38 publications

(27 citation statements)

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“…[25] On the other hand, when m e @ m g , there is a large solvatochromic shift in emission, [26,27] but almost no solvatochromic shift in absorption because only the instantaneous electronic polarization of the solvent can respond to the change in the molecular electrostatic potential upon excitation, and this property is almost the same for all organic solvents (n 2 % 2). [28] Push-pull conjugated compounds form an intermediate class. [29][30][31] Their ground-state dipole moments are large enough to induce a solvent polarization which interacts more strongly with the molecules in the excited state because the dipole moments are in the same direction and the excited-state dipole moment is larger, which explains why there is a modest solvatochromic shift in absorption.…”

Section: Discussionmentioning

confidence: 99%

Paradoxical Solvent Effects on the Absorption and Emission Spectra of Amino‐Substituted Perylene Monoimides

Zoon

Brouwer

2005

ChemPhysChem

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In N-(2,5-di-tert-butylphenyl)-9-pyrrolidinoperylene-3,4-dicarboximide (5PI) the absorption and emission spectra display large solvatochromic shifts, but, remarkably, the Stokes shift is practically independent of solvent polarity. This unique behavior is caused by the extraordinarily large ground-state dipole moment of 5PI, which further increases upon increasing the solvent polarity, whereas the excited-state dipole moment is less solvent dependent. In the corresponding piperidine compound, 6PI, this effect is much less important owing to the weaker coupling between the amino group and the aromatic imide moiety, and in the corresponding naphthalimide, 5NI, it is absent. The latter shows the conventional solvatochromic behavior of a push-pull substituted conjugated system, that is, minor shifts in absorption and a larger change in the emission energy with solvent polarity.

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Section: Discussionmentioning

confidence: 99%

Paradoxical Solvent Effects on the Absorption and Emission Spectra of Amino‐Substituted Perylene Monoimides

Zoon

Brouwer

2005

ChemPhysChem

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“…LRMS (low resolution mass spectrum) (EI) was recorded on a HP5989A mass spectrometer and HRMS (high resolution mass spectrum) (EI) on a Waters Micromass GCT mass spectrometer. Unknown compounds were determined by their 1 H NMR, 13 C NMR, MS and HRMS data. Compounds previously described in the literature were characterized by comparing their 1 H NMR spectra to published data.…”

Section: General Considerationsmentioning

confidence: 99%

A Facile Synthesis of N‐Aryl Substituted Piperidones

et al. 2009

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“…The concept of through-bond interactions (TBI) was introduced in 1968 by Hoffmann et al and describes the intramolecular interactions between functional groups non-conjugatively linked by orbital overlap. [6] Experimental evidence for TBI has been obtained from photoelectron and electronic spectroscopy as well as structural [7] and chemical studies. [8] Bi-and oligo(cyclohexylidenes) [9] are interesting candidates for use as spacers in DSA compounds, since their alternating s ± p ± s orbital topology allows the study of the influence of formally nonconjugated double bonds in the bridge on photoinduced charge-transfer phenomena.…”

Section: Introductionmentioning

confidence: 99%

Photoinduced Intramolecular Charge Separation in Donor/Acceptor-Substituted Bicyclohexylidene and Bicyclohexyl

et al. 2000

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The photophysical properties of a bicyclohexylidene (1DA) and a bicyclohexyl (2DA) substituted with an anilino electron donor and a dicyanoethylene electron acceptor have been studied. Quenching of local donor emission is observed for these compounds as well as quenching of the "pseudo-local" acceptor emission. Transient absorption spectra show dialkylanilino-type radical-cation and dicyanoethylene-type radical-anion absorptions. These results show that intramolecular charge separation takes place in 1DA and 2DA. This was corroborated by time-resolved microwave conductivity measurements from which large excited-state dipole moments were found for both 1DA and 2DA. Time-resolved fluorescence spectroscopy revealed that in the charge-separated state in cyclohexane for 2DA, molecular folding takes place on a nanosecond timescale. For 1DA in cyclohexane, either charge separation takes place in a (fully) folded conformation or very rapid (subnanosecond timescale) folding takes place subsequent to charge separation. In addition to this difference in conformational behavior, the presence of the exocyclic double bond between the cyclohexyl-type rings results in efficient quenching of the anilino donor triplet state and acceleration of the charge recombination rate by a factor of 20.

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Effect of through-bond interaction on conformation and structure of some N-arylpiperidone and N-aryltropanone derivatives. 2

Cited by 38 publications

References 0 publications

Paradoxical Solvent Effects on the Absorption and Emission Spectra of Amino‐Substituted Perylene Monoimides

Paradoxical Solvent Effects on the Absorption and Emission Spectra of Amino‐Substituted Perylene Monoimides

A Facile Synthesis of N‐Aryl Substituted Piperidones

Photoinduced Intramolecular Charge Separation in Donor/Acceptor-Substituted Bicyclohexylidene and Bicyclohexyl

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