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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

Solid-state EPR strategies for the structural characterization of paramagnetic NO adducts of frustrated Lewis pairs (FLPs)

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de Oliveira, Jr., Marcos [1] ; Wiegand, Thomas [2] ; Elmer, Lisa-Maria [3] ; Sajid, Muhammad [3] ; Kehr, Gerald [3] ; Erker, Gerhard [3] ; Magon, Claudio Jose [1] ; Eckert, Hellmut [1, 4]
Total Authors: 8
[1] Univ Sao Paulo, Inst Fis Sao Carlos, BR-13560970 Sao Paulo - Brazil
[2] ETH, Lab Phy Chem, CH-8049 Zurich - Switzerland
[3] WWU Munster, Inst Organ Chem, D-48149 Munster - Germany
[4] WWU Munster, Inst Phys Chem, D-48149 Munster - Germany
Total Affiliations: 4
Document type: Journal article
Source: Journal of Chemical Physics; v. 142, n. 12 MAR 28 2015.
Web of Science Citations: 9

Anisotropic interactions present in three new nitroxide radicals prepared by N, N addition of NO to various borane-phosphane frustrated Lewis pairs (FLPs) have been characterized by continuous-wave (cw) and pulsed X-band EPR spectroscopies in solid FLP-hydroxylamine matrices at 100 K. Anisotropic g-tensor values and B-11, N-14, and P-31 hyperfine coupling tensor components have been extracted from continuous-wave lineshape analyses, electron spin echo envelope modulation (ESEEM), and hyperfine sublevel correlation spectroscopy (HYSCORE) experiments with the help of computer simulation techniques. Suitable fitting constraints are developed on the basis of density functional theory (DFT) calculations. These calculations reveal that different from the situation in standard nitroxide radicals (TEMPO), the g-tensors are non-coincident with any of the nuclear hyperfine interaction tensors. The determination of these interaction parameters turns out to be successful, as the cw- and pulse EPR experiments are highly complementary in informational content. While the continuous-wave lineshape is largely influenced by the anisotropic hyperfine coupling to 14N and 31P, the ESEEM and HYSCORE spectra contain important information about the 11B hyperfine coupling and nuclear electric quadrupolar interaction. The set of cw- and pulsed EPR experiments, with fitting constraints developed by DFT calculations, defines an efficient strategy for the structural analysis of paramagnetic FLP adducts. (c) 2015 AIP Publishing LLC. (AU)

FAPESP's process: 13/23490-3 - Magnetic resonance techniques for the study of Structure/Property correlations in photonic glassy and glass ceramic materials
Grantee:Marcos de Oliveira Junior
Support type: Scholarships in Brazil - Post-Doctorate
FAPESP's process: 13/07793-6 - CEPIV - Center for Teaching, Research and Innovation in Glass
Grantee:Edgar Dutra Zanotto
Support type: Research Grants - Research, Innovation and Dissemination Centers - RIDC