Coordination chemistry
Pt TPE cages harvest light for cyclization
Open access · cc by · source: Europe PMC
Self-assembled platinum–tetraphenylethene cages transfer energy to rhodamine B (up to 77% ΦET) and photocatalyze maleimide–aniline cyclization in water-rich solvent.
How this study connects
Role on claims
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Self-assembled platinum–tetraphenylethene cages transfer energy to rhodamine B (up to 77% ΦET) and photocatalyze maleimide–aniline cyclization in water-rich solvent.
Evidence for the claim as stated.
Pt–TPE metallocages harvest light by AIE and FRET, then do chemistry. In 90% water/MeCN, emission boosts are 5-, 25- and 16-fold for 1b–3b with aggregate ΦF up to 25.67% (2b). ΦET is 77% (2b+RhB) and 58% (3b+RhB) at 5:1 donor/acceptor, with antenna effects 21 and 16. Photocatalysis: 97% of 6a with 2a+RhB in 12 h (92% with 3b+RhB; 74% even with bulky N-pyrenemaleimide). TPE–TPE separations are 9.1, 20.4 and 17.8 Å. Cage 1b is a weaker AIE/FRET platform.
Evidence for the claim as stated.
Turn-on sensing, turn-off sensing, FRET photocatalysis and photoluminescence quenching of a molecular catalyst are four fluorescence experiments. Ag/Au clusters raise ΦF 3.28% → 12.89% to report nM FQs; phage carbons quench to LOD 8.0 μM Fe³⁺; TB-Zn-CP quenches to 26.3 ppb picric acid; TPE cages donate to RhB (ΦET 77%/58%) to drive 97% cyclisation; Pt(II) PL quenching assigns oxidative quenching for >82% alkene CF₃ products. 'Fluorescence showed it worked' does not travel among those papers.
Evidence for the claim as stated.
Open questions
Tensions this paper is part of
From concept pages' “where studies disagree.” Disagreement means the same question; scope means different assays, populations, or outcomes.
Turn-on sensing, turn-off sensing, FRET photocatalysis and photoluminescence quenching of a molecular catalyst are four fluorescence experiments. Ag/Au clusters raise ΦF 3.28% → 12.89% to report nM FQs; phage carbons quench to LOD 8.0 μM Fe³⁺; TB-Zn-CP quenches to 26.3 ppb picric acid; TPE cages donate to RhB (ΦET 77%/58%) to drive 97% cyclisation; Pt(II) PL quenching assigns oxidative quenching for >82% alkene CF₃ products. 'Fluorescence showed it worked' does not travel among those papers.
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
Structured fields used in claim comparison tables when every cited study has a complete layer.
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.
Key findings
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.
Methodology
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.
Limitations
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.
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