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Conformational effects on high-spin organic molecules

Silverman, Scott K. and Dougherty, Dennis A. (1993) Conformational effects on high-spin organic molecules. Journal of Physical Chemistry, 97 (50). pp. 13273-13283. ISSN 0022-3654. https://resolver.caltech.edu/CaltechAUTHORS:20180601-145342001

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Abstract

The ability of m-phenylene to ferromagnetically couple spin-containing substituents that are substantially twisted out of conjugation is investigated. The "bis(TMM)" strategy is employed, in which two triplet TMM biradicals are linked through m-phenylene to produce relatively stable, organic tetraradicals that are characterized by EPR spectroscopy. Under conditions of moderate twisting (4), ferromagnetic coupling is seen, and the tetraradical has a quintet ground state. Severely twisting both TMMs as in 13 disrupts spin communication, and two noninteracting triplets are produced. This is in contrast to other highly twisted m-phenylene derivatives, in which antiferromagnetic coupling has been observed. Surprisingly, severely twisting only one TMM (14) still produces ferromagnetic coupling and a quintet ground state through a spin polarization mechanism analogous to that proposed for 90° twisted ethylene. Several ring-constrained TMMs (17-19) are investigated as models for more nearly planar systems.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1021/j100152a035DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/j100152a035PublisherSupporting Information
ORCID:
AuthorORCID
Dougherty, Dennis A.0000-0003-1464-2461
Additional Information:© 1993 American Chemical Society. Received: July 19, 1993. We thank the National Science Foundation for support of this work. S.K.S. thanks the NSF for a predoctoral fellowship.
Funders:
Funding AgencyGrant Number
NSF Predoctoral FellowshipUNSPECIFIED
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Arnold and Mabel Beckman Laboratories of Chemical Synthesis8825
Issue or Number:50
Record Number:CaltechAUTHORS:20180601-145342001
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180601-145342001
Official Citation:Conformational effects on high-spin organic molecules Scott K. Silverman and Dennis A. Dougherty The Journal of Physical Chemistry 1993 97 (50), 13273-13283 DOI: 10.1021/j100152a035
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86754
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:01 Jun 2018 22:46
Last Modified:03 Oct 2019 19:47

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