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@ARTICLE{PiechaBisiorek:188412,
author = {Piecha-Bisiorek, A. and Bator, G. and Sawka-Dobrowolska, W.
and Sobczyk, L. and Rok, M. and Medycki, W. and Schneider,
G. J.},
title = {{S}tructure and {T}unneling {S}plitting {S}pectra of
{M}ethyl {G}roups of {T}etramethylpyrazine in {C}omplexes
with {C}hloranilic and {B}romanilic {A}cids},
journal = {The journal of physical chemistry / A},
volume = {118},
number = {34},
issn = {1520-5215},
address = {Washington, DC},
publisher = {Soc.},
reportid = {FZJ-2015-01810},
pages = {7159 - 7166},
year = {2014},
abstract = {The crystal and molecular structure of the
2,3,5,6-tetramethylpyrazine (TMP) complex with
2,5-dibromo-3,6-dihydroxy-p-quinone (bromanilic acid, BRA)
has been studied and the results are compared with TMP CLA
(2,5-dichloro-3,6-dihydroxy-p-quinone (chloranilic acid,
CLA) complex. The X-ray structure of TMP BRA complex
indicates the formation of dimeric units, in which two
BRA– anions are connected by two O–H···O (2.646(2)
Å) hydrogen bonds, whereas the cations and anions are
joined together by strong N+–H···O– (2.657(2) Å)
hydrogen bonds. The results are analyzed in terms of both
the methyl group surroundings and the C–H···O and
N+–H···O– (or N···H–O) bridge formations. Both
effects, the strength of the N+–H···O– hydrogen bonds
and steric hindrance for the rotations, are responsible for
the CH3 group dynamics. For the TMP CLA and TMP BRA
complexes, the inelastic neutron backscattering spectra were
also investigated. In the case of TMP CLA, four tunneling
signals have been observed in the energy range ±30 μeV,
which indicates four inequivalent methyl groups in the
crystal structure at the lowest temperature. No tunneling
splitting is observed in the case of the TMP BRA complex,
most probably due to the overlapping with the elastic peak.
The tunneling results are consistent with the 1H NMR
spin–lattice relaxation time investigations in a wide
temperature range, which also point to the CH3 group
tunneling effect in the case of TMP CLA.},
cin = {JCNS (München) ; Jülich Centre for Neutron Science JCNS
(München) ; JCNS-FRM-II / Neutronenstreuung ; JCNS-1 /
ICS-1},
ddc = {530},
cid = {I:(DE-Juel1)JCNS-FRM-II-20110218 /
I:(DE-Juel1)JCNS-1-20110106 / I:(DE-Juel1)ICS-1-20110106},
pnm = {54G - JCNS (POF2-54G24)},
pid = {G:(DE-HGF)POF2-54G24},
experiment = {EXP:(DE-MLZ)SPHERES-20140101},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000341121000048},
pubmed = {pmid:25099129},
doi = {10.1021/jp5058429},
url = {https://juser.fz-juelich.de/record/188412},
}