Modular Core-Substituted Naphthalenediimide-Based Metal-Organic Frameworks for Red-Light-Driven Photocatalysis

Area of Science:

• Materials Science
• Photocatalysis
• Sustainable Chemistry

Background:

• Conventional UV and blue-light photocatalysis face limitations like shallow penetration and photodamage.
• Developing efficient red-light heterogeneous photocatalysts is challenging.
• Molecular engineering strategies for red-light photocatalysis are scarce.

Purpose of the Study:

• Design and synthesize novel isostructural metal-organic frameworks (MOFs) for efficient red-light photocatalysis.
• Investigate the performance of these MOFs in photocatalytic reactions.
• Elucidate the mechanism governing their photocatalytic activity.

Main Methods:

• Synthesis of two novel isostructural MOFs (NHEt-cNDI-Cu3 and SEt-cNDI-Cu3) based on core-substituted naphthalenediimide (cNDI) dyes.
• Characterization of MOF properties including surface area and stability.
• Evaluation of photocatalytic activity under red-light irradiation for sulfide oxidations and oxidative coupling of benzylamine.

Main Results:

• Both MOFs exhibited high surface area and good stability.
• NHEt-cNDI-Cu3 showed prominent photocatalytic activity under red light for specific reactions.
• SEt-cNDI-Cu3 exhibited significantly lower performance under red light compared to its analogue.
• Mechanistic studies indicated that the LUMO of cNDI-based MOFs dictates photocatalytic reactivity.

Conclusions:

• The designed cNDI-based MOFs show promise for long-wavelength photocatalysis.
• This work provides a new platform for molecular engineering of red-light photocatalysts.
• The findings contribute to the advancement of sustainable chemistry through efficient photocatalysis.