Enabling photocatalytic activity of [Ru(2,2′:6′,2′′-terpyridine)2]2+ integrated into a metal-organic framework

As a creation platform for multifunctional materials, crystalline metal-organic frameworks (MOFs) can integrate different chromophores through reticular chemistry to adjust their spatial arrangement and intermolecular interaction, in turn achieving the purpose of improving the nature of optoelectronic properties. Herein, a stepwise reticular synthesis approach is successfully used to construct a multicomponent MOF, in which the well-known bis-terpyridyl ruthenium chromophore is orderly arranged into the skeleton of the material. Remarkably, this method promotes the excited state lifetime of the bis-terpyridyl ruthenium core, by two orders of magnitude (from 0.39 to 22.09 ns), to the extent that it can produce singlet oxygen under visible light irradiation at room temperature. Meanwhile, the obtained multicomponent MOF has been established to have considerable porosity for exposure of substrates to the catalytic sites, rendering it suitable for heterogeneous photocatalysis, including as a photooxidation detoxifier for sulfur mustard simulant. Moreover, DFT and TDDFT calculations reveal that the synergistic charge transfer among different components in the MOF may play a crucial role in improving the excited state properties of the bis-terpyridyl ruthenium motif.

Automated summary

A stepwise reticular synthesis approach was used to construct a multicomponent MOF with orderly arranged chromophores, significantly improving the excited state properties of the material. DFT and TDDFT calculations suggest that synergistic charge transfer among different components in the MOF plays a crucial role in enhancing the optoelectronic properties of the material.