Temperature effects in solvatochromic shifts

Suppan, Paul; Tsiamis, Chris

doi:10.1039/f29817701553

Cited by 31 publications

(21 citation statements)

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“…Accompanied is a red shift of the peak maxima, which is larger in MCH (Δ λ f =11 nm) than in the acetonitrile/THF mixed solvent (Δ λ f =4 nm). This can be attributed to the increase of both ε and n with decreasing the temperature 26. A similar temperature‐dependent fluorescence behavior has also been observed for 1P in mixed acetonitrile/THF (9:1) 10…”

Section: Resultssupporting

confidence: 75%

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The N‐Arylamino Conjugation Effect in the Photochemistry of Fluorescent Protein Chromophores and Aminostilbenes

Huang¹,

Yang²

2010

Chemistry An Asian Journal

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To understand the nonradiative decay mechanism of fluorescent protein chromophores in solutions, a systematic comparison of a series of (Z)-4-(N-arylamino)benzylidene-2,3-imidazolinones (ABDIs: 2 P, 2 PP, 2 OM, and 2 OMB) and the corresponding trans-4-(N-arylamino)-4'-cyanostilbenes (ACSs: 1 P, 1 PP, 1 OM, and 1 OMB) was performed. We have previously shown that the parameter Phi(f)+2 Phi(tc), in which Phi(f) and Phi(tc) are the quantum yields of fluorescence and trans-->cis photoisomerization, respectively, is an effective probe for evaluating the contribution of twisted intramolecular charge transfer (TICT) states in the excited decays of trans-aminostilbenes, including the push-pull ACSs. One of the criteria for postulating the presence of a TICT state is Phi(f)+2 Phi(tc)<<1.0, because its formation is decoupled with the C=C bond (tau) torsion pathway and its decay is generally nonradiative. Our results show that the same concept also applies to ABDIs 2 with the parameter Phi(f)+2 Phi(ZE) in which Phi(ZE) is the quantum yield of Z-->E photoisomerization. We conclude that the tau torsion rather than the C-C bond (phi) torsion is responsible for the nonradiative decays of ABDIs 2 in aprotic solvents (hexane, THF, acetonitrile). The phenyl-arylamino C--N bond (omega) torsion that leads to a nonradiative TICT state is important only for 2 OM in THF and acetonitrile. If the solvent is protic (methanol and 10-20 % H(2)O in THF), a new nonradiative decay channel is present for ABDIs 2, but not for ACSs 1. It is attributed to internal conversion (IC) induced by solvent (donor)-solute (acceptor) hydrogen-bonding (HB) interactions. The possible HB modes and the concept of tau torsion-coupled proton transfer are also discussed.

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Section: Resultssupporting

confidence: 75%

“…This can be attributed to the increase of both e and n with decreasing the temperature. [26] A similar temperature-dependent fluorescence behavior has also been observed for 1 P in mixed acetonitrile/THF (9:1). [10] Quantum Yields and Lifetimes…”

Section: Shown Insupporting

confidence: 66%

The N‐Arylamino Conjugation Effect in the Photochemistry of Fluorescent Protein Chromophores and Aminostilbenes

Huang¹,

Yang²

2010

Chemistry An Asian Journal

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“…Usually, E T (30) or π * increases with decreasing T [1,68–70] . This consideration would apply to several results from literature [3c,68–70] …”

Section: Discussionmentioning

confidence: 94%

“…Generally, each of the various solvatochromic dyes requires another cavity volume (V probe ) and solvent cage shape within the solvent bulk. As suggested by Suppan, the absorption energy of the solvatochromic probe is a product of the solvent function with the function of the solute [3c] . For the solute function of the probe, Suppan considered the cavity radius ( a ) of the solvatochromic molecule and the dipole moment difference of ground and excited electronic state.…”

Section: Resultsmentioning

confidence: 99%

Reappraisal of Empirical Solvent Polarity Scales for Organic Solvents

et al. 2020

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Correlations of Reichardt's ET(30), the Catalán SdP (solvent dipolarity), SP (solvent polarizability), SA (solvent acidity), SB (solvent basicity), Kamlet‐Taft π* (dipolarity/polarizability), α (hydrogen bond donating ability) and β (hydrogen bond accepting ability) polarity parameters with the molar concentration of 161 pure organic solvents are presented. Mostly, linear relationships of the polarity parameter as a function of molar concentration are obtained as long as each individual solvent class is considered separately. A physically different interpretation of the ET(30), Kamlet‐Taft π* and α as well as Catalán SA and SB parameters has been proposed. Furthermore, the Hildebrand solubility parameter in combination with the diffraction index is used for the correlation analysis with the above‐mentioned solvent parameters. It can be concluded that empirical polarity parameters derived from solvatochromic UV/Vis measurements are inherently a function of the molecular structure of the probe.

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“…This can be an indicator of dipolar electronic transitions. 10 The Stark-derived Σβ 0 values for the series (Table 3, see ESI † for details of fitting and extraction of charge transfer parameters) follow a similar trend to HRS β 0 , although measurement and fitting uncertainties are large and in all cases values are larger than HRS β 0 -a common observation in prior work. 5b,7,11 Similar to 3, the fit of the main low energy peak in 2 consists of three Gaussians, each at slightly higher energy than those of 3.…”

mentioning

confidence: 76%