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Coordination chemistry

Pt TPE cages harvest light for cyclization

Kumar A, Saha R, Mukherjee PS · Chemical science · 2021

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.

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.

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.

How this study connects

Role on claims

Each row is a claim on a concept or method page where this paper supports, challenges, or qualifies the statement. Roles are hand-checked — not a model guess.

  • SupportsCoordination chemistryconcept

    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

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