A MOF that merges Cu and Ru photocatalysis
CR–BPY1 places copper ions next to a Ru-substituted polyoxometalate so N-phenyl-THIQ and ketones couple under an 18 W lamp with pore size-selectivity.
Source
Merging of the photocatalysis and copper catalysis in metal-organic frameworks for oxidative C-C bond formation
Inspect source passages
A MOF that merges Cu and Ru photocatalysis
These passages occur verbatim in the stored paper text. They support the points listed below; they do not verify every statement in the explanation.
Nitromethane coupling gave 90% yield after 24 h irradiation.
The resulting reaction gave a yield of 90% after 24 hours irradiation.
Reuse dropped the yield from 90% to 82% after three cycles.
Solids of CR– BPY 1 could be isolated from the reaction suspension by simple filtration alone and reused at least three times with moderate loss of activity (from 90% to 82% of yield after three cycles).
What they did
Authors built a copper–bipyridine MOF encapsulating [SiW11O39Ru(H2O)]5−, then ran oxidative couplings of N-phenyl-tetrahydroisoquinoline with nitromethane or acetophenone under household fluorescent light.
What they found
Nitromethane coupling gives 90% yield in 24 h and recycles 90→82% over three runs. Filtration stops the reaction (true heterogeneous). A bulky ketone gives <10% conversion because it cannot enter the channels. Homogeneous Cu or POM controls give only 25–42%.
The limits
What it doesn't show
A broad substrate table beyond a few amines/ketones and long-term flow operation are not provided; grinding to 2 μm only modestly speeds the reaction.
Key terms
- CR–BPY1
- Copper–bipyridine MOF containing a Ru-substituted Keggin polyoxometalate.
- Dual catalysis
- Ru photocatalysis makes an iminium; Cu activates the nucleophile in the same pore.
- Size selectivity
- Bulky ketones that exceed the channel size barely react.
- Iminium intermediate
- Oxidized tertiary amine that is trapped by a carbon nucleophile.
- Polyoxometalate
- Metal-oxide cluster; here [SiW11O39Ru(H2O)]5− is the photo site.
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The MOF merges:
Common questions
What light is enough?
An 18 W fluorescent lamp.
Nitromethane coupling yield?
90% after 24 h; 82% after three recycles.
Is it heterogeneous?
Yes—filtration after 18 h nearly stops further conversion.
Why is a bulky ketone slow?
It is larger than the MOF channels (<10% conversion).
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