1994
DOI: 10.1021/j100092a002
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Picosecond Dynamics of Cation-Macrocycle Interactions in the Excited State of an Intrinsic Fluorescence Probe: The Calcium Complex of 4-(N-Monoaza-15-crown-5)-4'-phenylstilbene

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Cited by 66 publications
(43 citation statements)
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“…46,52 The addition of acid to form ReAZBAP + -H + , or of metal salts to form ReAZBAP + -M n+ , results in a blue-shift in the ILCT band ( Figure 1 and Table 1; Figure S1 in Supporting Information), with the largest shift occurring on protonation. Such shifts are well-documented for chromophores linked to azacrown ethers, [23][24][25]31,36,54 and they are attributed to the interaction of the cation with the azacrown nitrogen atom increasing its oxidation potential, 46 raising the energy of the ILCT transition, and giving a shift in peak wavelength (∆λ) whose magnitude correlates broadly with the charge-to-radius 55 (z/r) ratios of the cations (Figure 1, inset). An obvious anomaly in the general trend is Li + that, despite its high z/r ratio, gives a small shift that has been attributed to this small cation binding to the four azacrown oxygen atoms and remaining relatively remote from the azacrown N-atom.…”
Section: Resultsmentioning
confidence: 79%
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“…46,52 The addition of acid to form ReAZBAP + -H + , or of metal salts to form ReAZBAP + -M n+ , results in a blue-shift in the ILCT band ( Figure 1 and Table 1; Figure S1 in Supporting Information), with the largest shift occurring on protonation. Such shifts are well-documented for chromophores linked to azacrown ethers, [23][24][25]31,36,54 and they are attributed to the interaction of the cation with the azacrown nitrogen atom increasing its oxidation potential, 46 raising the energy of the ILCT transition, and giving a shift in peak wavelength (∆λ) whose magnitude correlates broadly with the charge-to-radius 55 (z/r) ratios of the cations (Figure 1, inset). An obvious anomaly in the general trend is Li + that, despite its high z/r ratio, gives a small shift that has been attributed to this small cation binding to the four azacrown oxygen atoms and remaining relatively remote from the azacrown N-atom.…”
Section: Resultsmentioning
confidence: 79%
“…58 The binding constants obtained for ReAZBAP + are low within the range of values reported for these respective metal cations with other aza-15-crown-5 chromophores; 23,36,54,57,59,60 this effect is attributable to an azacrown N-atom that carries a partial positive charge as a result of its linkage to an electron-accepting Re I group within the positively charged ReAZBAP + . The variation in the magnitude of K with metal cation does not correlate with the bandshifts, as is also reported for other azacrown sensors, but the trend observed here is similar to that for other aza-15-crown-5 systems; 36,51,61 it has been rationalized through a combination of several effects including size-matching between azacrown and cation, cation desolvation thermodynamics, and the nature of the interaction between these hard cations and the hard oxygen and soft nitrogen atoms of the azacrown.…”
Section: Resultsmentioning
confidence: 82%
“…Photoinduced recoordination manifests itself as the presence of two fluorescent forms emitting at different wavelengths. The experimental evidence of this phenomenon can be found in7–18. Recoordination should be taken into account when the experimental spectra of arylazacrown‐containing dyes and their complexes are interpreted.…”
Section: Introductionmentioning
confidence: 95%
“…The change of the characteristic fluorescence emission of DMABN with the concentration of metal cations has been investigated in a number of theoretical 22, 23 and experimental 24–26 studies. As a matter of fact, fluorescent sensors in which reversible binding of a molecule or ion is accompanied by an emission shift are much sought after because they allow the measurement of the recognized species from the intensity ratio at two emission wavelengths with opposite substrate‐sensitivity responses 27.…”
Section: Introductionmentioning
confidence: 99%
“…Unfortunately, on complexation by cations, the majority of the chromo‐ and fluoroionophores show hypsochromic shifts of the absorption spectra, while the emission spectra are only slightly blue‐shifted as a result of the breaking of the cation‐chromophore bond in the excited states. Fluorescent probes 25 with chemically tailored sensitivity can be obtained in principle by coupling a chromophore with two fluorescing excited states of considerably different charge‐transfer character and a ionophore including the electron‐donor substituent: the complexed cation is able to decrease the charge‐transfer process and hence the corresponding emission. The addition of alkali or alkaline‐earth perchlorates to DMABN‐Crown5 in acetonitrile solution shifts the absorption maximum to higher energies.…”
Section: Introductionmentioning
confidence: 99%