Solvatomorphism of Reichardt's dye

Pike, Sarah J.; Bond, Andrew D.; Hunter, Christopher A.

doi:10.1039/c8ce00480c

Cited by 16 publications

(28 citation statements)

References 26 publications

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“…The X-ray crystal structural analysis shows that the interplanar angles between the anion and the cation moieties (φ DA ) of 2b (71.6°), 3b (68.9°), and 4b (84.8°) are larger than that of 1b containing Et 2 O (55.7°). 57 As expected, φ DA of 4b is larger than those of 2b and 3b, indicating that the steric hindrance affects the interplanar angle (Figure 3a,c,d). The φ DA of 22 (88.7°), the precursor of 3b (Figure 3b), is larger than that of 3b, indicating that the phenoxide moiety of 3b, having a higher HOMO energy level than the phenol moiety of 22, is essential for achieving small ΔE D−A and the interaction between the donor and the acceptor moieties.…”

Section: ■ Results and Discussionsupporting

confidence: 68%

Section: Resultsmentioning

confidence: 70%

“…1b•H 2 SO 4 (1.452 Å) and 1b containing Et 2 O (1.451 Å) also have similar r DA . 57,58 These results indicate that 1a, 2a, 3a, and 4a have identical electronic structures with different ΔE D−A and φ DA , and thus, are suitable to discuss the influence of ΔE D−A and φ DA on E int and ΔE H−L .…”

Section: ■ Results and Discussionmentioning

confidence: 79%

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HOMO–LUMO Energy-Gap Tuning of π-Conjugated Zwitterions Composed of Electron-Donating Anion and Electron-Accepting Cation

et al. 2020

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π-Conjugated molecules with small highest occupied molecular orbital (HOMO)−lowest unoccupied molecular orbital (LUMO) energy gaps (ΔE H−L ) have been extensively studied because of their unique optoelectronic properties. Although the expansion of πconjugation is one of the well-known approaches for designing molecules with small ΔE H−L values, such an approach inevitably gives large πconjugated molecules sometimes suffering from synthetic difficulty and low solubility toward organic solvents. To develop relatively small donor− acceptor molecules with small ΔE H−L values, we have designed and synthesized π-conjugated zwitterions composed of electron-donating anions, such as phenoxide and anthroxide, and electron-accepting cations, such as pyridinium and acridinium. The energy difference between the HOMO of the anion and the LUMO of the cation (ΔE D−A ) and the interplanar angle between them (φ DA ) have a crucial effect on ΔE H−L , and hence, on the electronic structures and optoelectronic properties of these zwitterions. The zwitterions with small ΔE D−A and large φ DA have a small ΔE H−L of ca. 1 eV and show amphoteric redox properties and near-infrared (NIR) electronic absorption exceeding λ = 1000 nm. The NIR absorption responds to solvent polarity, temperature, and acid addition. This molecular design will generate small π-conjugated donor−acceptor molecules with small ΔE H−L values.

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Section: ■ Results and Discussionsupporting

confidence: 68%

Section: Resultsmentioning

confidence: 70%

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HOMO–LUMO Energy-Gap Tuning of π-Conjugated Zwitterions Composed of Electron-Donating Anion and Electron-Accepting Cation

et al. 2020

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“…The regression coefficients of Table show that the solvatochromism of all probes is most sensitive to the solvent’s Lewis acidity. This result agrees with the 1 H and 13 C NMR data of the solvation of p -RB in CDCl 3 , DMSO- d 6 , and (CD 3 ) 2 CO, with the result of an X-ray study of the p -RB hydrate, and with our 1 H NMR data for p -CB in CD 3 OD and CD 3 CN (Table ). A change from the former to the latter solvent involves elimination of hydrogen bonding to the phenolate oxygen, and introduction of shielding/deshielding of the probe’s hydrogens by the anisotropic triple bond of CD 3 CN.…”

Section: Resultssupporting

confidence: 91%

Understanding Solvation: Comparison of Reichardt’s Solvatochromic Probe and Related Molecular “Core” Structures

et al. 2019

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The compound 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl)phenolate, p-RB, shows distinct colors in different solvents (solvatochromism). The compound 4-(pyridinium-1-yl)phenolate, p-CB, represents the part of p-RB which is responsible for this phenomenon. We compared the solvatochromism of both compounds and also the structurally related 2-(pyridinium-1-yl)phenolate, o-CB, and (2,4-dimethyl-6-(2,4,6-triphenyl-N-pyridinium-1-yl)phenolate, o-RB. In pure solvents, plots of the empirical solvent polarity parameter [E T (probe), kcal/mol] of the different probes correlate linearly with slopes close to unity. That is, these probes are similarly sensitive to specific and nonspecific interactions with the solvents. The solvatochromism of p-CB and o-CB was studied, for the first time, in binary mixtures of water with dimethyl sulfoxide (DMSO) and 1-propanol (1-PrOH). The dependence of E T (probe) on mixture composition was nonideal due to preferential solvation of the probe by one component of the binary solvent mixture. We treated our solvatochromic data using a solvent-exchange model that considers formation of the complex solvents [HOH•••OS(CH 3 ) 2 ] and [HOH•••O(H)-C 3 H 7 ]. The model applies satisfactorily to our data and shows the importance to solvation of hydrogen-bonding and hydrophobic interactions. The preferential solvation of (more hydrophobic) p-RB is more pronounced than that of p-CB or o-CB. The solvent complex [OH 2 •••O(H)-C 3 H 7 ] is more efficient than [OH 2 ••• OS(CH 3 ) 2 ] because of more possibilities of hydrogen bonding.

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“…10,56 It is possible that the observed dependence of the adoption of cis-and trans-4 in the solid state, on the nature of the solvent employed in the crystallisation conditions, could in a similar manner be influenced by the differing nature of the solventsolute interactions present in solution for each isomer. 57 However, it should be noted that attempts to derive direct correlation between the solution and solid state behaviour of these systems is challenging and complex due to complications from a number of factors, including the crystal packing forces observed in the solid state, that are often so delicately balanced and governed by a wide range of influences. Further in-depth solvent screening studies of this system are required to ascertain the role of the solvent in the crystallisation conditions on the adoption of the azodioxy dimers.…”

Section: Influence Of Weakly Electron-donating Ortho-substituentsmentioning

confidence: 99%

ortho-Substituent effect on the crystal packing and solid state speciation of aromaticC-nitroso compounds

2020

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Solvatomorphism of Reichardt's dye

Abstract: Six different crystal structures are obtained depending on the crystallization solvent.

Cited by 16 publications

References 26 publications

HOMO–LUMO Energy-Gap Tuning of π-Conjugated Zwitterions Composed of Electron-Donating Anion and Electron-Accepting Cation

HOMO–LUMO Energy-Gap Tuning of π-Conjugated Zwitterions Composed of Electron-Donating Anion and Electron-Accepting Cation

Understanding Solvation: Comparison of Reichardt’s Solvatochromic Probe and Related Molecular “Core” Structures

ortho-Substituent effect on the crystal packing and solid state speciation of aromaticC-nitroso compounds

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