Reaction amplification with a gain: Triplet exciton–mediated quantum chain using mixed crystals with a tailor-made triplet sensitizer
Reaction amplification with a gain: Triplet exciton–mediated quantum chain using mixed crystals with a tailor-made triplet sensitizer
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带增益的反应放大：使用带有定制三重态敏化剂的混合晶体的三重态激子介导的量子链
DOI：
10.1073/pnas.2401982121
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发表时间：
2024
期刊：
影响因子：
--
通讯作者：
Garcia-Garibay, Miguel A.
中科院分区：
文献类型：
--
作者：
Paul, Indrajit;Konieczny, Krzysztof A.;Chavez, Roberto;Garcia-Garibay, Miguel A.
结晶杜瓦苯 (DB) 二酸单阴离子盐与作为分子内三重态能量敏化剂的苯乙酮连接的哌嗪鎓阳离子 (DB-AcPh-Pz) 的光化学价键异构化表现出量子链反应，每个吸收的光子产生多达 450 个产物分子 (Φ ≈ 450)。相比之下，缺乏三重态敏化剂的乙苯连接的哌嗪鎓的DB二酸单盐(DB-EtPh-Pz)的同晶晶体表现出不太令人印象深刻的量子产率，约为100%。 Φ ≈ 22。为了确定三重态激发态载流子在绝热光化学反应中的至关重要性，我们制备了 DB-AcPh-Pza 的混合晶体，作为 DB-EtPh-Pz 晶体中的稀释三重态敏化剂客体。正如从它们的高度结构相似性所预期的那样，在0.1%至10%范围内的三重态敏化剂盐很容易形成固溶体。在光被三重态敏化剂连接的DB-AcPh-Pz吸收的条件下进行的实验可用于引发从3DB-AcPh-Pz到3HB*-AcPh-Pz的三重态绝热反应，该反应可以作为链载体并将能量转移到未反应的DB-EtPh-Pz，其中晶体固溶体中的激子离域可以帮助进行有效的能量转移并使得使用光产物的量子链成为可能三重链载体。用低至 0.1% 的三重态敏化剂激发混合晶体即可产生极高的量子产率 Φ ≈ 517。
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 theDBdiacid 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 withDB-AcPh-Pzas a dilute triplet sensitizer guest in crystals ofDB-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-linkedDB-AcPh-Pzcan be used to initiate a triplet state adiabatic reaction from3DB-AcPh-Pzto3HB*-AcPh-Pz, which can serve as a chain carrier and transfer energy to an unreactedDB-EtPh-Pzwhere 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.