Pt TPE cages harvest light for cyclization
Self-assembled platinum–tetraphenylethene cages transfer energy to rhodamine B (up to 77% ΦET) and photocatalyze maleimide–aniline cyclization in water-rich solvent.
Source
Self-assembled metallasupramolecular cages towards light harvesting systems for oxidative cyclization
Study at a glance
- Design
- Other — Pt–TPE metallacages as AIE donors for FRET to RhB and photo-oxidative cyclization
- N
- Supramolecular photocatalysis — no sample N
- Population
- Pt4L2/Pt8L2 TPE cages with rhodamine B acceptors
- Outcome
- Energy-transfer efficiency and visible-light oxidative cyclization yields
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Inspect source passages
Pt TPE cages harvest light for cyclization
These passages occur verbatim in the stored paper text. They support the points listed below; they do not verify every statement in the explanation.
Ligand L is isolated in 67% yield
Desired ligand L was synthesized by allylic coupling of imidazole with 1,1,2,2-tetrakis(4-(bromomethyl)phenyl)ethene C1 in the presence of a base in 67% yield (Scheme S1).
Antenna effects are 21 and 16 for the two LHSs
Both the LHSs (( 2b + RhB ) and ( 3b + RhB )) showed good antenna effect of 21 and 16, respectively.
What they did
They made tetraimidazole TPE donor L (67%) and assembled it with 180°/120° trans-Pt acceptors into Pt4L2 and Pt8L2 cages, exchanged to PF6 salts, and studied AIE in 90% water/MeCN. Cages 2b/3b donated FRET to RhB; the pair catalyzed visible-light oxidative cyclization of N,N-dimethylaniline with maleimides.
What they found
AIE: 5-, 25-, and 16-fold emission boosts for 1b–3b; aggregate ΦF up to 25.67% (2b). ΦET is 77% (2b+RhB) and 58% (3b+RhB) at 5:1 donor/acceptor; antenna effects 21 and 16. Photocatalysis: 97% of 6a with 2a+RhB (12 h), 92% with 3b+RhB, 74% even with bulky N-pyrenemaleimide. TPE–TPE separations 9.1, 20.4, and 17.8 Å.
The limits
What it doesn't show
Energy-transfer efficiencies are for one solvent ratio and one dye. Cage 1b is a weaker AIE/FRET platform. Yields are for a specific cyclization, not a general photoredox scope. DFT geometries are gas-phase models, not crystal structures of the assemblies.
Key terms
- AIE
- Aggregation-induced emission: TPE fluoresces when propeller rotation is blocked in aggregates.
- FRET
- Through-space dipole energy transfer from cage emission to RhB absorption.
- Metallacage
- 3D coordination assembly; here Pt4L2 or Pt8L2 prisms from a tetratopic donor.
- Antenna effect
- How much acceptor emission is amplified by the donor relative to direct acceptor excitation.
- TPE
- Tetraphenylethene, the AIE-active core of ligand L.
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Maximum FRET efficiency (2b + RhB, 5:1) is about
Common questions
Why 90% water/MeCN?
Maximum AIE, stable nano-aggregates, and no self-quenching precipitation on the FRET timescale.
Who is the FRET acceptor?
Rhodamine B, whose absorption overlaps cage emission.
Does the harvested energy do chemistry?
Yes—photo-oxidative cyclization of dimethylaniline with maleimides in up to 97% yield.
Cage 2 vs 3?
2b has higher ΦET (77% vs 58%) and antenna effect (21 vs 16).
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