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Coordination Nanosheets Based on Terpyridine-Zinc(II) Complexes: As Photoactive Host Materials
Takamasa Tsukamoto1,2, Kenji Takada1, Ryota Sakamoto1,3
1Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Journal of the American Chemical Society
|March 22, 2017
Summary
New photoluminescent coordination nanosheets (CONASHs) using terpyridine ligands and zinc ions exhibit diverse structures and tunable photofunctions. These materials show potential for advanced applications due to their unique optical properties and anion-exchange capabilities.
Area of Science:
- Materials Science
- Supramolecular Chemistry
- Photochemistry
Background:
- Photoluminescent coordination nanosheets (CONASHs) offer tunable properties through ligand design and coordination.
- Terpyridine (tpy) ligands and zinc(II) ions are key components for constructing functional nanomaterials.
Purpose of the Study:
- To synthesize and characterize diverse tpy-zinc(II) CONASHs with varying structures and photofunctions.
- To investigate the impact of ligand structure and counteranions on the photophysical properties of CONASHs.
- To explore the potential of CONASHs in applications such as anion exchange and exciton migration.
Main Methods:
- Synthesis of CONASHs via liquid/liquid interfacial reaction between terpyridine ligands and zinc salts.
- Structural characterization using techniques sensitive to coordination modes and anion interactions.
- Photophysical measurements, including luminescence spectroscopy and solvatochromism studies.
Main Results:
- Two distinct tpy-zinc(II) CONASHs were synthesized: a cationic 1-Zn with a bis(tpy)Zn motif and a neutral 1-Zn2(SO4)2 with a [Zn2(μ-O2SO2)2(tpy)2] motif, differing in anion coordination.
- Luminescence color varied from blue (480 nm) for 1-Zn to yellow (552 nm) for 1-Zn2(SO4)2, with the latter exhibiting solvatoluminochromism.
- Modification of the tpy ligand (ligand 2) resulted in a red-shifted orange emission (590 nm) for 2-Zn.
- Cationic CONASHs (1-Zn and 2-Zn) demonstrated anion exchange capacity, successfully incorporating anionic xanthene dyes and facilitating exciton migration.
Conclusions:
- The structure and photofunctions of tpy-zinc(II) CONASHs are highly tunable by altering ligand design and the nature of coordinating anions.
- These CONASHs exhibit promising photophysical properties, including variable luminescence and solvatochromism.
- The demonstrated anion exchange and exciton migration capabilities highlight the potential of tpy-zinc(II) CONASHs as versatile photofunctional nanomaterials.
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