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Competing phenol–imidazole and phenol–phenol interactions in the flexible supramolecular environment of N,N′-bis(3-imidazol-1-ylpropyl)naphthalenediimide causing domain expansion
Ist Teil von
New journal of chemistry, 2017, Vol.41 (19), p.10750-10760
Erscheinungsjahr
2017
Quelle
Alma/SFX Local Collection
Beschreibungen/Notizen
The relevance of a fundamentally important imidazole⋯phenol interaction in the self-assembly of cocrystals and a salt of a bis-imidazole hinged through a flexible tether to a naphthalenediimide, namely
N
,
N
′-bis(3-imidazol-1-ylpropyl)naphthalenediimide (
L
), with a series of phenolic compounds is studied. Cocrystals of
L
with phenolic compounds, 1,2-dihydroxybenzene (
cat
), 1,3-dihydroxybenzene (
res
), and 1,3,5-trihydroxybenzene (
phi
), namely
L·cat
,
L·(res)2
,
L·phi·H2O
, and a salt with 2,4-dinitrophenol (
dnp
),
L2+·(dnp−)2
, are structurally characterized. Hierarchical effects of oxime-imidazole synthons in the cocrystal of
L
with 2,3-dihydroxyphenylaldoxime,
L·(dhpa)2
, are also investigated. The cocrystals of
L
with
cat
and
phi
are formed in a 1 : 1 molar ratio, but the latter is a hydrated cocrystal. Compound
L
adopts a C-like shape in cocrystals
L·cat
and
L·phi·H2O
, whereas
L
adopts an S-like shape in the
L·(res)2
cocrystal. It adopts an I-like shape in the salt
L2+·(dnp−)2
or in the cocrystal
L·(dhpa)2
. Analyses of cocrystals of
L
with these phenolic compounds show a significant presence of charge-transfer interactions between naphthalenediimide only with
phi
. Phenol⋯imidazole interactions together with C–H⋯N
(imidazole)
and N⋯π interactions cause domain expansion in
L·cat
by forming dimeric sub-assemblies providing C-like geometry to
L
. In this example, one of the flexible arms bearing imidazole is crystallographically disordered, and a low temperature
1
H-NMR study reveals conformational changes. In contrast, in the case of
L·phi·H2O
, domain expansion that takes place due to the interplay of charge-transfer, imidazole⋯phenol and phenol⋯water interactions provides a C-like shape to
L
. In these cases, phenol⋯phenol interactions have less relevance. In the case of the 1 : 2 salt
L2+·(dnp−)2
, imidazolium⋯phenolate interactions dominate and provide a stretched geometry to
L
, whereas competition to form homodimers between oximes and oxime⋯imidazole interactions predominates in the cocrystal
L·(dhpa)2
. This cocrystal has a stretched structure of
L
. In the lattice of this cocrystal, phenol⋯phenol interactions are not relevant. Cocrystal
L·res
is identified as one exception among the series where competition between phenol⋯phenol with phenol⋯imidazole interactions results in domain expansion facilitating an interpenetrated structure.
Sprache
Englisch
Identifikatoren
ISSN: 1144-0546
eISSN: 1369-9261
DOI: 10.1039/C7NJ02322G
Titel-ID: cdi_crossref_primary_10_1039_C7NJ02322G
Format
–
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