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Volumn 15, Issue 31, 2009, Pages 7534-7538

Electrochemically induced intermolecular anion transfer

Author keywords

Devices; Luminescence; Macrocycles; Molecular; Molecular recognition; Voltammetry

Indexed keywords

ANION RECEPTOR; ANION TRANSFER; DEVICES; ELECTROCHEMICAL REDUCTIONS; ELECTROCHEMICAL STIMULUS; EMISSION INTENSITY; EQUIMOLAR CONCENTRATIONS; FERROCENE; FERROCENIUM; MACROCYCLES; MACROCYCLIC; MOLECULAR; MULTI-STEP; NMR TUBES; SIGNALING UNITS; SPECTROELECTROCHEMICAL; SYNTHETIC PATHWAYS;

EID: 68049104326     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200900878     Document Type: Article
Times cited : (8)

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    • We decided to use a solvent with a moderate dielectric constant, such as acetone, in order to minimize the effect of the ion-pair dissociation equilibria, but without reaching a highly competitive solvation which would hinder the host-guest interaction. J. W. Jones, HW. Gibson, J. Am. Chem. Soc. 2003, 125, 7001. The use of anions as their tetrabutylammonium (TBA) salts also makes possible to assume that this bulky countercation will not form very tight ion pairs.
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    • Binding constants were calculated by non-linear regression of the titration isotherm using the SPECFIT/32 software
    • Binding constants were calculated by non-linear regression of the titration isotherm using the SPECFIT/32 software.
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    • -5M).
    • -5M).
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    • Blank experiments revealed that the emission of 1 was not affected by the presence of 2 under our experimental conditions, 1, 2, 5×10 -5M in acetone: λexc, 400nm, Thus, we consider that the major cause for the above mentioned emission quenching process would be the removal of lhe anion from 1. See the Supporting Information
    • exc.,=400nm). Thus, we consider that the major cause for the above mentioned emission quenching process would be the removal of lhe anion from 1. See the Supporting Information.
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    • For a ternary mixture of 1, 2 and TBAbenzoate (A, in equimolar concentration (5×10-5M) in acetone, having assumed a total dissociation of the TBAbenzoate ion pair (ref, 13, the two equilibria to be studied are: 1+A-&rlarr2; 1A, K 1A) and 2+A- &rlarr2; 2A, K 2A, Using the equations of binding constants and mass balances of all the species in solution, we can calculate the concentration of free anion by solving: K1AK2A[A, 3+(K1A+K2A+K1AK2A[1] tot)[A-]2+[A, A, tot= 0. See the Supporting Information. There seems to be a mismatch between the predicted anion distribution and the spectroscopic results which might be due to a secondary process occurring in solution. This is currently under study and it will r
    • tot= 0. See the Supporting Information. There seems to be a mismatch between the predicted anion distribution and the spectroscopic results which might be due to a secondary process occurring in solution. This is currently under study and it will reported in due course.
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    • We assume that compound 2 has been completely oxidised to 2, Therefore, the later and 1 are the two receptors taking part in the anion binding equilibria
    • +. Therefore, the later and 1 are the two receptors taking part in the anion binding equilibria.


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