A Novel Fluorophore with Dual Fluorescence: Local Excited State and Photoinduced Electron-Transfer-Promoted Charge-Transfer State

• Published in: Chemphyschem 2004-08, Vol.5 (8), p.1200-1209
• Main Authors: Thiagarajan, Viruthachalam, Selvaraju, Chellappan, Malar, E. J. Padma, Ramamurthy, Perumal
• Format: Article
• Language: English
• Subjects: ab initio calculations; Atomic and molecular physics; donor-acceptor systems; electron transfer; Exact sciences and technology; fluorescence; Fluorescence and phosphorescence spectra; Fluorescence and phosphorescence; radiationless transitions, quenching (intersystem crossing, internal conversion); Molecular properties and interactions with photons; Physics; sensors
• ISSN: 1439-4235; 1439-7641
• DOI: 10.1002/cphc.200400064

Absorption and emission spectra of 9‐N,N‐dimethylaniline decahydroacridinedione (DMAADD) have been studied in different solvents. The fluorescence spectra of DMAADD are found to exhibit dual emission in aprotic solvents and single emission in protic solvents. The effect of solvent polarity and viscosity on the absorption and emission spectra has also been studied. The fluorescence excitation spectra of DMAADD monitored at both the emission bands are different. The presence of two different conformation of the same molecule in the ground state has lead to two close lying excited states, local excited (LE) and charge transfer (CT), and thereby results in the dual fluorescence of the dye. A CT state involving the N,N‐dimethylaniline group and the decahydroacridinedione chromophore as donor and acceptor, respectively, has been identified as the source of the long wavelength anomalous fluorescence. The experimental studies were supported by ab initio time dependent‐density functional theory (TD‐DFT) calculations performed at the B3LYP/6–31G* level. The molecule possesses photoinduced electron transfer (PET) quenching in the LE state, which is confirmed by the fluorescence lifetime and fluorescent intensity enhancement in the presence of transition metal ions. Fluorescence goes both ways: Dual emitting decahydroacridinedione dye (DMAADD) is a new fluorescent probe for transition metal ions by fluorescence enhancement via photoinduced electron transfer. The photoinduced electron transfer from the donor to the excited state of ADD produces a low‐lying intramolecular charge‐transfer state (see graphic), which results in an anomalous longer wavelength emission.