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Multi-stimuli-responsive Zn()-Schiff base complexes adjusted by rotatable aromatic rings
Ist Teil von
Dalton transactions : an international journal of inorganic chemistry, 2021-11, Vol.5 (45), p.1683-1689
Ort / Verlag
Cambridge: Royal Society of Chemistry
Erscheinungsjahr
2021
Quelle
Alma/SFX Local Collection
Beschreibungen/Notizen
Multifunctional luminescent materials have attracted intensive interest. However, the mechanisms behind them are still to be explored. In this work, three Zn(
ii
) complexes based on Schiff bases (HL
1
and HL
2
) that contain rotatable aromatic rings were designed and prepared. They exhibited different mechanochromic luminescence (MCL) and acidochromism. The polymorphous ZnL
1
2
and ZnL
1a
2
crystallize in different crystal systems with different conformations. The ligands in ZnL
1
2
adopt a more twisted conformation than those in ZnL
1a
2
. ZnL
1
2
exhibits MCL with high contrast, while ZnL
1a
2
exhibits a negligible MCL property. This may be due to the looser packing of the complex induced by the more twisted conformation of the ligand HL
1
. ZnL
1
2
could undergo crystal phase transformation into ZnL
1a
2
by grinding/fuming cycles. To increase the flexibility of the ligand, a methylene group was introduced to result in HL
2
, which can improve the mechanochromic luminescence effect of the Zn(
ii
) complex with high color contrast. The ligands involved in coordination generally adopt a more twisted conformation than those free ligands due to the steric hindrance, resulting in more obvious MCL for complexes. By comparing the luminescence of ligands and their complexes under acid-base stimulation, it is found that the acidochromic properties could be attributed to the generation of ligands at the surface of complexes
via
the gaseous HCl-solid Zn(
ii
) complex reaction. The high contrast mechanochromic and acidochromic luminescence properties would lead to promising potential applications of these complexes in smart fluorescent materials, and would also provide some ideas for the design of multi-stimuli responsive molecules.
Three Zn(
ii
)-Schiff base complexes showed mechanochromic and acidochromic luminescence properties. ZnL
1
2
could undergo crystal phase transformation into ZnL
1a
2
by grinding/fuming cycles.