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  • Reaction amplification with a gain: Triplet exciton–mediated quantum chain using mixed crystals with a tailor-made triplet sensitizer
Title: Reaction amplification with a gain: Triplet exciton–mediated quantum chain using mixed crystals with a tailor-made triplet sensitizer
Photochemical valence bond isomerization of a crystalline Dewar benzene 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 (F ≈ 450). By contrast, isomorphous crystals of the Dewar benzene diacid monosalt of an ethylbenzene-linked piperazinium (DB-EtPh-Pz) lacking a triplet sensitizer showed a less impressive quantum yield of ca. F ≈ 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 the 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 a little as 0.1% triplet sensitizer resulted in an extraordinarily high quantum yield F ≈ 517.  more » « less
Award ID(s):
2154210
PAR ID:
10499905
Author(s) / Creator(s):
; ; ;
Date Published:
Journal Name:
Proceedings of the National Academy of Sciences
Volume:
121
Issue:
14
ISSN:
0027-8424
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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