Metal

Catalysis

Adsorption

Photosensitizer

Turnover number

Photochemistry

SBus

Eosin Y

Medicinal chemistry

Combinatorial chemistry

Organic chemistry

Photoredox catalysis

Metal-organic framework

Chemistry

Photocatalysis

Bifunctional

Journal of the American Chemical Society

Here we report the design of a bifunctional metal–organic layer (MOL), Hf-EY-Fe, by bridging eosin Y (EY)-capped Hf6 secondary building units (SBUs) with Fe-TPY (TPY = 4′-(4-carboxyphenyl)[2,2′:6′,2′′-terpyridine]-5,5′′-dicarboxylate) ligands. With the organic dye EY as an efficient photosensitizer and TPY-Fe(OTf)2 as the catalytic center, Hf-EY-Fe efficiently catalyzes aminotrifluoromethylation, hydroxytrifluoromethylation, and chlorotrifluoromethylation of alkenes. Hf-EY-Fe also catalyzes the synthesis of CF3-substituted derivatives of large bioactive molecules such as rotenone, estrone, and adapalene with sizes of up to 2.2 nm. The proximity between EY and iron centers and their site isolation in Hf-EY-Fe enhance catalytic activity while inhibiting their mutual deactivation, leading to high turnover numbers of up to 1840 and good recyclability of the MOL catalyst.

Bifunctional Metal–Organic Layer with Organic Dyes and Iron Centers for Synergistic Photoredox Catalysis