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On the Limited Stability of BDPA Radicals

On the Limited Stability of BDPA Radicals


Title: On the Limited Stability of BDPA Radicals
Author: Mandal, Sucharita
Sigurdsson, Snorri   orcid.org/0000-0003-2492-1456
Date: 2020-05-12
Language: English
Scope: 7486-7491
University/Institute: Háskóli Íslands
University of Iceland
School: Verkfræði- og náttúruvísindasvið (HÍ)
School of Engineering and Natural Sciences (UI)
Department: Raunvísindadeild (HÍ)
Faculty of Physical Sciences (UI)
Raunvísindastofnun (HÍ)
Science Institute (UI)
Series: Chemistry – A European Journal;26(33)
ISSN: 0947-6539
1521-3765 (eISSN)
DOI: 10.1002/chem.202001084
Subject: BDPA; Dynamic nuclear polarization; EPR spectroscopy; Radical stability; Radicals; Kjarnsýrur; Litrófsgreining; Skautun (rafsegulfræði)
URI: https://hdl.handle.net/20.500.11815/1974

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Citation:

Mandal, S., & Sigurdsson, S. T. (2020). On the limited stability of BDPA radicals. Chemistry - A European Journal, 26(33), 7486-7491. doi: 10.1002/chem.202001084

Abstract:

1,3‐Bis(diphenylene)‐2‐phenylallyl (BDPA)‐based radicals are of interest as polarizing agents for dynamic nuclear polarization (DNP). For this purpose, a BDPA‐nitroxide biradical, employing a phosphodiester linkage, was synthesized. Contrary to what is commonly assumed, BDPA‐derived radicals were observed to have limited stability. Hence, the effects of various factors on the stability of BDPA radicals were investigated. Solvent polarity was found to play a significant role on degradation; a polar BDPA radical was observed to degrade faster in a non‐polar solvent, whereas non‐polar radicals were more unstable in polar solvents. The rate of decomposition was found to increase non‐linearly with increasing radical concentration; a 2‐fold increase in concentration led to a 3‐fold increase in the rate of degradation. Collectively, these results indicate that the dimerization is a significant degradation pathway for BDPA radicals and indeed, a dimer of one BDPA radical was detected by mass spectrometry.

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This is the peer reviewed version of the following article: [Mandal, S., & Sigurdsson, S. T. (2020). On the limited stability of BDPA radicals. Chemistry - A European Journal, 26(33), 7486-7491. doi: 10.1002/chem.202001084], which has been published in final form at https://doi.org/10.1002/chem.202001084. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.

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