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Seeking Small Molecules for Singlet Fission: A Heteroatom Substitution Strategy
- Source :
- Journal of the American Chemical Society. 136:12638-12647
- Publication Year :
- 2014
- Publisher :
- American Chemical Society (ACS), 2014.
-
Abstract
- We design theoretically small molecule candidates for singlet fission chromophores, aiming to achieve a balance between sufficient diradical character and kinetic persistence. We develop a perturbation strategy based on the captodative effect to introduce diradical character into small π-systems. Specifically, this can be accomplished by replacing pairs of not necessarily adjacent C atoms with isoelectronic and isosteric pairs of B and N atoms. Three rules of thumb emerge from our studies to aid further design: (i) Lewis structures provide insight into likely diradical character; (ii) formal radical centers of the diradical must be well-separated; (iii) stabilization of radical centers by a donor (N) and an acceptor (B) is essential. Following the rules, we propose candidate molecules. Employing reliable multireference calculations for excited states, we identify three likely candidate molecules for SF chromophores. These include a benzene, a napthalene, and an azulene, where four C atoms are replaced by a pair of B and a pair of N atoms.
- Subjects :
- Diradical
Chemistry
Heteroatom
02 engineering and technology
General Chemistry
Azulene
010402 general chemistry
021001 nanoscience & nanotechnology
01 natural sciences
Biochemistry
Captodative effect
Catalysis
0104 chemical sciences
Lewis structure
symbols.namesake
chemistry.chemical_compound
Colloid and Surface Chemistry
Computational chemistry
Excited state
Singlet fission
symbols
Molecule
0210 nano-technology
Subjects
Details
- ISSN :
- 15205126 and 00027863
- Volume :
- 136
- Database :
- OpenAIRE
- Journal :
- Journal of the American Chemical Society
- Accession number :
- edsair.doi.dedup.....c3625fd58dfc26cd36d7aa04c157d566