Solvent-Driven Multiply Configurable On/Off Fluorescent Indicator of the pH Window: A Diethylenetriamine Bearing Two End Pyrene Fragments
- 20 April 2007
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Physical Chemistry B
- Vol. 111 (19), 5090-5100
- https://doi.org/10.1021/jp0689823
Abstract
Fluorescence behaviors of a simple-structured molecule (L), a diethylenetriamine bearing two end pyrene fragments, have been investigated in water. Effects of adding a less-polar organic solvent (acetonitrile: MeCN) on the emission behaviors have been studied by means of steady-state and time-resolved fluorescence measurements. L dissolved in water shows dual-mode fluorescence consisting of monomer and excimer emissions. The monomer emission shows an "on-off" intensity profile against the pH window (pH 2-12), whereas the excimer emission shows an "off-on" profile. Upon MeCN addition, the monomer emission maintains the "on-off" profile. In contrast, the "off-on" profile of the excimer emission is drastically changed: L shows two more types of profiles, "off-on-off-on" and "off-on-off", along with the MeCN concentration increase, thus behaving as a multiply configurable fluorescent indicator of the pH window. The MeCN-driven excimer emission switching of L is triggered by (i) the decrease in stability of the intramolecular ground-state dimer (GSD) formed between the end pyrene fragments, which suppresses the direct photoexcitation of GSD (suppression of the "static" excimer formation), leading to a decrease in the excimer emission intensity at basic pH; and (ii) the decrease in polarity of solution, which allows formation of a "dynamic" excimer via a monomer-to-excimer transition, resulting in an enhancement of the excimer emission intensity at acidic-neutral pH.Keywords
This publication has 78 references indexed in Scilit:
- Solvent effect on the photophysical properties of 4-phenoxy-N-methyl-1,8-naphthalimideJournal of Photochemistry and Photobiology A: Chemistry, 2006
- Highly Fluorescent Contrast for Rewritable Optical Storage Based on Photochromic Bisthienylethene-Bridged Naphthalimide DimerChemistry of Materials, 2005
- Bis-azamacrocyclic Anthracene as a Fluorescent Chemosensor for Cations in Aqueous SolutionThe Journal of Physical Chemistry B, 2005
- pH Responsive Eu(III)−Phenanthroline Supramolecular Conjugate: Novel “Off−On−Off” Luminescent Signaling in the Physiological pH RangeJournal of the American Chemical Society, 2003
- Supramolecular interactions of hexacyanocobaltate(III) with polyamine receptors containing a terminal anthracene sensorJournal of Photochemistry and Photobiology A: Chemistry, 2003
- Focus Article: Molecules that add upChemical Communications, 2002
- Ground- and Excited-State Aggregation Properties of a Pyrene Derivative in Aqueous MediaThe Journal of Physical Chemistry A, 2001
- Solvatochromic shifts of naphthalene and pyrene excimersJournal of Photochemistry and Photobiology A: Chemistry, 1994
- Photophysics of preassociated pyrenes in aqueous polymer solutions and in other organized mediaChemical Reviews, 1993
- Time-resolved monomer and excimer fluorescence of 1,3-di(1-pyrenyl)propane at different temperatures: no evidence for distributions from picosecond laser experiments with nanosecond time resolutionThe Journal of Physical Chemistry, 1991