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Developing Photosensitizer-Cobaloxime Hybrids for Solar-Driven H2 Production in Aqueous Aerobic Conditions
Published on: October 5, 2019
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Through-Space Charge Transfer Complexes Based on Terpyridine Bi-Functionalization for Efficient Solar-Driven H2O2
Manman Dai1, Ningxu Han1, Xiang Li2
1State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, Jilin, 130012, P.R. China.
Angewandte Chemie (International Ed. in English)
|December 18, 2025
Summary
Researchers developed a terpyridine functionalization strategy for precise control over donor-acceptor stacking, enhancing through-space charge transfer (TSCT) for efficient photocatalysis. This led to a new material with double the H2O2 production efficiency compared to a previous design.
Area of Science:
- Supramolecular Chemistry
- Materials Science
- Photocatalysis
Background:
- Precise control over molecular stacking is crucial for optimizing charge transfer in functional materials.
- Terpyridine scaffolds offer versatile platforms for designing complex supramolecular architectures.
- Donor-acceptor (D-A) interactions are key to efficient photocatalytic processes.
Purpose of the Study:
- To develop a novel terpyridine bi-functionalization strategy for precise spatial control of D-A stacking.
- To optimize through-space charge transfer (TSCT) for enhanced photocatalytic efficiency.
- To investigate the structure-property relationships in Zn(II) complexes with tunable TSCT.
Main Methods:
- Designed and synthesized two terpyridine-based ligands (L1, L2) functionalized with donor (triphenylamine) and acceptor (triphenyltriazine) units.
- Coordinated ligands with Zn(II) to form complexes (S1, S2) with distinct D-A stacking geometries.
- Characterized complexes using spectroscopic and electrochemical methods to evaluate TSCT, charge carrier dynamics, and photocatalytic activity.
Main Results:
- Achieved precise molecular-level editing of D-A stacking, resulting in slip-stacked (S1) and co-facial (S2) geometries.
- The co-facial complex (S2) exhibited significantly enhanced TSCT, leading to improved visible-light absorption and charge carrier lifetime.
- S2 demonstrated superior charge separation efficiency and achieved a photocatalytic efficiency of 2063 µmol g⁻¹ h⁻¹ for H₂O₂ production, twice that of S1, without sacrificial agents.
Conclusions:
- The terpyridine bi-functionalization strategy enables tunable TSCT and precise control over D-A stacking in supramolecular systems.
- The designed Zn(II) complexes show great potential as efficient photocatalysts for H₂O₂ production.
- This work provides valuable insights for the rational design of advanced supramolecular photocatalytic materials.
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