Aromatic acylation of hydroxy groups via the rare S  N 1 reaction pathway

Bayliss, Mark; Homer, Roger B.; Shepherd, Martin J.

doi:10.1039/c39900000305

Cited by 22 publications

(30 citation statements)

References 3 publications

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“…Due to the high symmetry of the dimer the two diabatic electronic configurations of the CT states, M + M − and M − M + , are coupled so that no real charge localization can take place. The second reason for our findings can be explained by Bayliss law about solvatochromic shifts in spherical cavities,

Δ E^{normale normalx} \sim \frac{μ^{2}}{R^{3}} \cdot \frac{n^{2} - 1}{{2 n}^{2} + 1}

with

R

the radius of a spherical cavity and

n

the refractive index. Bayliss law predicts that the energy shift is proportional to the square of the transition dipole moment µ, that is, the bright Frenkel state with a large transition dipole moment is expected to show a larger shift compared with the CT state with

μ \approx 0

.…”

Section: Resultsmentioning

confidence: 84%

Influence of a polarizable surrounding on the electronically excited states of aggregated perylene materials

et al. 2016

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To tune the efficiency of organic semiconductor devices it is important to understand limiting factors as trapping mechanisms for excitons or charges. An understanding of such mechanisms deserves an accurate description of the involved electronical states in the given environment. In this study, we investigate how a polarizable surrounding influences the relative positions of electronically excited states of dimers of different perylene dyes. Polarization effects are particularly interesting for these systems, because gas phase computations predict that the CT states lie slightly above the corresponding Frenkel states. A polarizable environment may change this energy order because CT states are thought to be more sensitive to a polarizable surrounding than Frenkel states. A first insight we got via a TD-HF approach in combination with a polarizable continuum model (PCM). These give limited insights because TD-HF overestimates excitation energies of CT states. However, SCS-CC2 approaches, which are sufficiently accurate, cannot easily be used in combination with continuum solvent models. Hence, we developed two approaches to combine gas phase SCS-CC2 results with solvent effects based on TD-HF computations. Their accuracies were finally checked via ADC(2)//COSMO computations. The results show that for perylene dyes a polarizable surrounding alone does not influence the energetic ordering of CT and Frenkel states. Variations in the energy order of the states only result from nuclear relaxation effects after the excitation process. © 2016 Wiley Periodicals, Inc.

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Δ E^{normale normalx} \sim \frac{μ^{2}}{R^{3}} \cdot \frac{n^{2} - 1}{{2 n}^{2} + 1}

with

R

the radius of a spherical cavity and

n

μ \approx 0

.…”

Section: Resultsmentioning

confidence: 84%

Influence of a polarizable surrounding on the electronically excited states of aggregated perylene materials

et al. 2016

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“…Bases such as triethylamine or pyridine could not be used, since steric hindrance of the carbonyl position by the anthracene moiety leads to the formation of stable quaternary acylammonium salts that are hardly reactive towards alcohols, severely lowering the yield when tertiary amines are added. 18 Similarly, the non-functional aromatic amide 15 was synthesized by adding two equivalents of butylamine to 13 in dichloromethane.…”

Section: Synthesis Of Anthracene Derivativesmentioning

confidence: 99%

“…To obtain pure 6-(anthracen-9-yloxy) hexan-1-ol 17 (8.2 g, 54 %) as a yellow-orange oil, the dried mixture was purified via chromatography on silica (eluent: dichloromethane/hexane); R f (CH 2 Cl 2 /hexane) 0.16; 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 1.50-1.60 (m, 2H, CH 2 CH 2 CH 2 ), 1.65-1.77 (m, 4H, CH 2 CH 2 CH 2 ), 2.08 (quin, J=7. 5 (18) In a 2 L flask equipped with a Dean-Stark water separator, 12.0 g anthrone (61.7 mmol, 1 eq) was dissolved in 1 L toluene. 1,12-dodecanediol (125 g, 617 mmol, 10 eq) and 2.5 mL sulfuric acid (≥ 95 %) were added and the solution was heated to reflux.…”

Section: -(Dodec-11-en-1-yl)anthracene (10)mentioning

confidence: 99%

Synthesis and evaluation of 9-substituted anthracenes with potential in reversible polymer systems

et al. 2016

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“…We apply the resulting formulation to analyze free energetics of electron transfer ͑ET͒ reactions 4,5 and solvent spectral shifts associated with electronic spectroscopy [6][7][8][9][10] in the quadrupolar solvents. We consider both one and two-sphere cavity descriptions for solute molecules to examine the solvent reorganization free energy and free energy of reaction for ET.…”

Section: Introductionmentioning

confidence: 99%

A continuum theory of solvation in quadrupolar solvents. II. Solvation free energetics, dynamics, and solvatochromism

Jeon

Kim

2003

The Journal of Chemical Physics

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The continuum theory of solvation developed in the preceding paper ͓J. Chem. Phys. 119, 8606 ͑2003͔͒ is applied to study free energetics and dynamics relevant to charge shift processes in polarizable quadrupolar solvents in the Born-Oppenheimer regime of solvent electronic degrees of freedom. The outer-sphere solvent reorganization free energy and free energy of reaction for electron transfer systems are investigated in both one and two-sphere cavity descriptions. The quadrupolar susceptibility needed in the theory is determined using recent Stokes shift measurements by Reynolds et al. ͓J. Phys. Chem. 100, 10337 ͑1996͔͒. A good accord with measurements and molecular theory estimates of the solvent reorganization free energy for bridged donor-acceptor systems is obtained. The solvatochromic shifts associated with chromophores are examined with a first-order perturbation method. The application of the theory to electronic absorption of betaine in the quadrupolar solvents yields a good agreement with the E T (30) solvent polarity scale. By incorporating the collective motions associated with solvent quadrupoles, the theory is extended to study inertial solvation dynamics. In contrast with dipolar liquids, the solvent frequency in the quadrupolar solvents increases as the multipole character of the solute charge distribution increases. This is in accord with a recent molecular dynamics simulation result for supercritical CO 2 .

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Aromatic acylation of hydroxy groups via the rare S N 1 reaction pathway

Cited by 22 publications

References 3 publications

Influence of a polarizable surrounding on the electronically excited states of aggregated perylene materials

Influence of a polarizable surrounding on the electronically excited states of aggregated perylene materials

Synthesis and evaluation of 9-substituted anthracenes with potential in reversible polymer systems

A continuum theory of solvation in quadrupolar solvents. II. Solvation free energetics, dynamics, and solvatochromism

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