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1.
Chem Commun (Camb) ; 60(55): 7085-7088, 2024 Jul 04.
Artículo en Inglés | MEDLINE | ID: mdl-38896476

RESUMEN

Nanorotor R1 (420 kHz) was assembled from five components utilizing three orthogonal interactions. Post-modification at the distal position generated the advanced six component rotor R2 (45 kHz). The decrease in R2 speed leads to the inhibition of a three-component reaction by reducing catalyst release.

2.
Proc Natl Acad Sci U S A ; 121(14): e2401982121, 2024 Apr 02.
Artículo en Inglés | MEDLINE | ID: mdl-38536753

RESUMEN

Photochemical valence bond isomerization of a crystalline Dewar benzene (DB) diacid monoanion salt with an acetophenone-linked piperazinium cation that serves as an intramolecular triplet energy sensitizer (DB-AcPh-Pz) exhibits a quantum chain reaction with as many as 450 product molecules per photon absorbed (Φ ≈ 450). By contrast, isomorphous crystals of the DB diacid monosalt of an ethylbenzene-linked piperazinium (DB-EtPh-Pz) lacking a triplet sensitizer showed a less impressive quantum yield of ca. Φ ≈ 22. To establish the critical importance of a triplet excited state carrier in the adiabatic photochemical reaction we prepared mixed crystals with DB-AcPh-Pz as a dilute triplet sensitizer guest in crystals of DB-EtPh-Pz. As expected from their high structural similarities, solid solutions were easily formed with the triplet sensitizer salt in the range of 0.1 to 10%. Experiments carried out under conditions where light is absorbed by the triplet sensitizer-linked DB-AcPh-Pz can be used to initiate a triplet state adiabatic reaction from 3DB-AcPh-Pz to 3HB*-AcPh-Pz, which can serve as a chain carrier and transfer energy to an unreacted DB-EtPh-Pz where exciton delocalization in the crystalline solid solution can help carry out an efficient energy transfer and enable a quantum chain employing the photoproduct as a triplet chain carrier. Excitation of mixed crystals with as little as 0.1% triplet sensitizer resulted in an extraordinarily high quantum yield Φ ≈ 517.

3.
Dalton Trans ; 53(8): 3454-3458, 2024 Feb 20.
Artículo en Inglés | MEDLINE | ID: mdl-38305461

RESUMEN

When the slider-on-deck [Cu3(1)(2)]3+ and guest G were treated with palladium(II) ions, the biped 2 was released from [Cu3(1)(2)]3+ generating the nanocage [Pd2(2)4(G)]4+ with guest G being encapsulated (NetState-II). This transformation that was reversed by the addition of DMAP enabled modulation of both the overall fluorescence and the activity of copper(I) catalyzing an aza Hopf cyclization.

4.
J Am Chem Soc ; 146(4): 2435-2444, 2024 Jan 31.
Artículo en Inglés | MEDLINE | ID: mdl-38251983

RESUMEN

To increase information density and security in communication, Nature at times encodes signals in the time domain, for instance, Ca2+ ion signals. Double encoding in the time domain operates beyond this level of security because the data are encoded in two time-dependent output signals showing distinct periods, frequencies, and full duration half-maxima. To illustrate such a protocol, a three-component ensemble consisting of a double ion-selective luminophore with two distinct receptor sites, hexacyclen, and diaza-18-crown-6 ether is demonstrated to act as a logic AND gate with Ag+ and Ca2+ ions as inputs. The gate shows an unprecedented 2-fold time-encoded fluorescence output at 590 and 488 nm based on metal ion pulses with distinct periods when trichloroacetic acid is applied as chemical fuel.

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