Intramolecular excimer fluorescence, its solvent dependence, and photodimerization of 1,2-dianthrylethanes

doi:10.1016/0009-2614(76)80050-4

Chemical Physics Letters

Volume 38, Issue 3, 15 March 1976, Pages 599-601

https://doi.org/10.1016/0009-2614(76)80050-4 Get rights and content

Abstract

Both 1,2-di(1-anthryl)ethane (I) and 1,2-di(9-anthryl) ethane (II) show two types of excimer fluorescence spectra under different conditions; one with peak at 460 nm (type-1) and the other with peak at 530 nm (type-2). Furthermore, the type-1 excimer emission shows a peculiar dependence upon the solvent polarity.

References (10)

R. Livingston et al.
J. Am. Chem. Soc.
(1967)
F. Hirayama
J. Chem. Phys.
(1965)
E.A. Chandross et al.
J. Am. Chem. Soc.
(1970)
F. Schneider et al.
Ber. Bunsenges. Physik. Chem.
(1968)
F. Schneider et al.
Ber. Bunsenges. Physik. Chem.
(1970)
N. Nakashima, M. Murakawa and N. Mataga, Bull. Chem. Soc. Japan, to be...

There are more references available in the full text version of this article.

Cited by (44)

Synthesis and Photochemical Properties of Axially Chiral Bis(dinaphthofuran)
2018, Journal of Organic Chemistry
Both enantiomers of axially chiral bis(dinaphthofuran) were prepared in only two steps from 1′-hydroxy-4′-methoxy-2,2′-binaphthalenyl-1,4-dione, followed by optical resolution via high-performance liquid chromatography (HPLC) using a chiral stationary phase (CSP). The absolute configurations were determined by comparison of experimental and calculated vibrational circular dichroism (VCD) spectra. Synthetic bis(dinaphthofuran) exhibited a broad and unstructured emission derived from an intramolecular excimer in both solution and solid state. The methylene bridge brings both chromophores close to each other and induces significant changes in the photophysical behavior. Chiral bis(dinaphthofuran) displayed a bathochromic shift in emission, as compared to the racemic mixture in the solid state. Furthermore, the compounds showed high circularly polarized luminescence (CPL) with a dissymmetry factor (g_lum) of 10^–3 at 405 nm upon excitation at 265 nm in a methanol solution. This compound serves as a model for the design and synthesis of organic materials having CPL activity.
Temperature dependence of the multiple fluorescence of 9,9′-dianthrylmethanol
1998, Chemical Physics
Temperature- and solvent polarity-dependent fluorescence spectra and decay curves of 9,9′-dianthrylmethanol are analysed using global analysis. The spectra can be decomposed into three contributions which are assigned to an anthracene-type, an excimer and a charge transfer (CT) species. The latter shows significant red-shifts with increasing solvent polarity and gains in relative importance upon lowering the temperature. It reaches a maximum at 200 K in n-butyronitrile where the excimer component is already negligible. These findings are interpreted with the possibility of small-overlap and large-overlap molecular conformations. In addition to these three emitting states, at least two quenching channels (photoproduct and intramolecular exciplex) have to be taken into account.
Multiple emitting species and competing intramolecular fluorescence quenching in 9,9′-dianthrylmethanol and model compounds
1995, Chemical Physics Letters
In addition to the anthracene-type emission, 9,9′-dianthrylmethanol (A1_OHA) shows a structureless long-wavelength fluorescence band, which undergoes a red-shift as well as an increase of its relative intensity with increasing solvent polarity. A parallel intramolecular fluorescence quenching process is investigated by the study of two reference compounds, 9-hydroxymethylanthracene and 9-ethoxymethylanthracene. In spite of the lack of the additional fluorescence band in this case, the quenching still persists. It might be caused by the formation of an intramolecular nonemissive exciplex but it cannot be the source for the observed additional red-shifted structureless emission band of the bichromophoric compound. The latter has been accounted for by a polar excited state product resulting from a charge separation process.
Fluorescence spectra and geometry of 1,2-bis(9-acetoxy-10-anthryl)-ethane
1994, Journal of Photochemistry and Photobiology, A: Chemistry
The fluorescence and fluorescence excitation spectra of 9-acetoxy-10-methyl-anthracene (AMA) and 1,2-bis(9-acetoxy-10-anthryl)-ethane (AAEA, a dimer of AMA) in various solvents were observed at room temperature. Using a simple procedure, the fluorescence spectra of AAEA were resolved into four fluorescent components: one structured fluorescence band (F1), a less structured fluorescence band (F2) and two broad and structureless fluorescence bands (F3 and F4). F1 and F2 are emissions from the trans and gauche forms. F3 and F4 are excimer fluorescences and are formed via a charge transfer state. The excited state dipole moment of AAEA is estimated to be approximately 18 D.
Excimer geometries in bichromophoric molecules: A theoretical and experimental study of 1,2-(bis-9-anthryl)-ethane
1991, Chemical Physics
A detailed study of the photophysics and photochemistry of the bichromophoric molecule 1,2-(bis-9-anthryl)-ethane (A2A) is presented. The ground- and excited-state potential energy hypersurfaces of A2A were calculated using semiempirical methods modified to account for the facile intramolecular excimer formation observed in this molecule. Temperature dependent fluorescence spectra were numerically resolved into the contributions from various underlying components using principal factor analysis. Thesesteady state results were combined with both time resolved experiments and the semiempirical calculations to identify and characterize the various excimer geometries.
Picosecond laser photolysis studies on dimer model systems in relation to photosynthetic charge separation processes
1989, Tetrahedron
In relation to the photoinduced charge separation in the special pair of photosynthetic reaction center, solvation induced intramolecular electron transfer in the excited state of composite system with identical halves have been investigated with picosecond spectroscopy in the case of 1,2-dienthrylethanes. The energy gap dependences of charge separation and charge recombination in these systems are demonstrated and compared with those of hybrid dimer model of metal porphyrins, porphyrin-quinone systems and various aromatic donor-acceptor systems. The significance of these results in the understanding of efficient charge separation in biological reaction center is discussed.

View all citing articles on Scopus

View full text

Intramolecular excimer fluorescence, its solvent dependence, and photodimerization of 1,2-dianthrylethanes

Abstract

J. Am. Chem. Soc.

J. Chem. Phys.

J. Am. Chem. Soc.

Ber. Bunsenges. Physik. Chem.

Ber. Bunsenges. Physik. Chem.