Cyclo-biphenalenyl biradicaloid molecular materials: conformation, rearrangement, magnetism, and thermochromism
Abstract
Cyclo-biphenalenyl biradicaloid molecular materials with chair- and boat-conformations are studied by restricted and broken-symmetry DFT using the M06 family of meta-GGA functionals. The global minima of these molecular materials are magnetically silent due to the sigma-bond connecting the two phenalenyls, while the sigma-bond may undergo low-barrier sigmatropic rearrangements via pi-pi bonded paramagnetic intermediates. The validation of theory is performed for the chair-conformation by comparing the sigma-bonded structures and the rearrangement barriers with experimental data. The boat-conformation is then studied using the validated functional. The electronic spectra of both chair- and boat-conformations are calculated and their applications in thermochromism are discussed.
- Authors:
-
- ORNL
- Georgetown University
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). National Center for Computational Sciences (NCCS)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 986808
- DOE Contract Number:
- DE-AC05-00OR22725
- Resource Type:
- Conference
- Resource Relation:
- Conference: 9th Interational Symposium on Functional pi-Electron Systems, Atlanta, GA, USA, 20100523, 20100528
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; MOLECULES; MOLECULAR STRUCTURE; DENSITY FUNCTIONAL METHOD; CHEMICAL BONDS; MAGNETISM; ELECTRONIC STRUCTURE
Citation Formats
Huang, Jingsong, Sumpter, Bobby G, Meunier, Vincent, Tian, Yong-Hui, and Kertesz, Prof. Miklos. Cyclo-biphenalenyl biradicaloid molecular materials: conformation, rearrangement, magnetism, and thermochromism. United States: N. p., 2010.
Web.
Huang, Jingsong, Sumpter, Bobby G, Meunier, Vincent, Tian, Yong-Hui, & Kertesz, Prof. Miklos. Cyclo-biphenalenyl biradicaloid molecular materials: conformation, rearrangement, magnetism, and thermochromism. United States.
Huang, Jingsong, Sumpter, Bobby G, Meunier, Vincent, Tian, Yong-Hui, and Kertesz, Prof. Miklos. 2010.
"Cyclo-biphenalenyl biradicaloid molecular materials: conformation, rearrangement, magnetism, and thermochromism". United States.
@article{osti_986808,
title = {Cyclo-biphenalenyl biradicaloid molecular materials: conformation, rearrangement, magnetism, and thermochromism},
author = {Huang, Jingsong and Sumpter, Bobby G and Meunier, Vincent and Tian, Yong-Hui and Kertesz, Prof. Miklos},
abstractNote = {Cyclo-biphenalenyl biradicaloid molecular materials with chair- and boat-conformations are studied by restricted and broken-symmetry DFT using the M06 family of meta-GGA functionals. The global minima of these molecular materials are magnetically silent due to the sigma-bond connecting the two phenalenyls, while the sigma-bond may undergo low-barrier sigmatropic rearrangements via pi-pi bonded paramagnetic intermediates. The validation of theory is performed for the chair-conformation by comparing the sigma-bonded structures and the rearrangement barriers with experimental data. The boat-conformation is then studied using the validated functional. The electronic spectra of both chair- and boat-conformations are calculated and their applications in thermochromism are discussed.},
doi = {},
url = {https://www.osti.gov/biblio/986808},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Fri Jan 01 00:00:00 EST 2010},
month = {Fri Jan 01 00:00:00 EST 2010}
}