Article ; Online: Excited-state dynamics of Wurster's salts.
The journal of physical chemistry. A
2012 Volume 116, Issue 28, Page(s) 7516–7522
Abstract: The excited-state dynamics of a series of Wurster's salts (p-phenylenediamine radical cations) with different subtituents on the nitrogen atoms was investigated under a variety of experimental conditions using a combination of ultrafast spectroscopic ... ...
| Abstract | The excited-state dynamics of a series of Wurster's salts (p-phenylenediamine radical cations) with different subtituents on the nitrogen atoms was investigated under a variety of experimental conditions using a combination of ultrafast spectroscopic techniques. At room temperature, the lifetime of the lowest excited state of all radical cations is on the order of 200 fs, independently of the solvent, that is, water, nitriles, alcohols, and room-temperature ionic liquid. On the other hand, all cations, except that with the bulky nitrogen substituents, become fluorescent below 120 K. The observed dynamics can be accounted for by the presence of a conical intersection between the D(1) and D(0) states. For the cations with a small nitrogen substituent, this conical intersection could be accessed through a twist of one amino group, as already suggested for Wurster's Blue. However, this coordinate cannot be invoked for the cation with bulky nitrogen subtituents, and more probably, pyramidalization of the nitrogen center and/or deformation of the phenyl ring play an important role. Consequently, the excited-state dynamics of these structurally very similar Wurster's salts involves different decay mechanisms. |
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| MeSH term(s) | Free Radicals/chemistry ; Molecular Structure ; Phenylenediamines/chemistry ; Quantum Theory ; Salts/chemistry |
| Chemical Substances | Free Radicals ; Phenylenediamines ; Salts ; 4-phenylenediamine (U770QIT64J) |
| Language | English |
| Publishing date | 2012-07-19 |
| Publishing country | United States |
| Document type | Journal Article ; Research Support, Non-U.S. Gov't |
| ISSN | 1520-5215 |
| ISSN (online) | 1520-5215 |
| DOI | 10.1021/jp3045548 |
| Database | MEDical Literature Analysis and Retrieval System OnLINE |
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