Exceptionally Long Lifetimes of Strongly Entangled Acyl–Trityl Radical Pairs Photochemically Generated in Crystalline Trityl Ketones,Journal of the American Chemical Society

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Exceptionally Long Lifetimes of Strongly Entangled Acyl–Trityl Radical Pairs Photochemically Generated in Crystalline Trityl Ketones
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-01-04 , DOI: 10.1021/jacs.2c11787
Vince M Hipwell ₁ , Alana Rose Meyer ₁ , Miguel A Garcia-Garibay ₁

Affiliation

Triplet acyl–alkyl radical pairs generated by pulsed laser excitation within the constraints of their nanocrystalline ketone precursors were recently introduced as a potential platform for the robust and repeated instantiation of spin qubit pairs for applications in quantum information science. Here, we report the transient spectroscopy of a series of nanocrystalline trityl–alkyl and trityl–aryl ketones capable of generating correlated triplet radical pairs with persistent triphenylmethyl radicals forced to remain within bonding distances of highly reactive acyl radicals. Whereas triplet trityl–acyl radical pairs decay by competing product-forming decarbonylation and intersystem crossing, triplet trityl–benzoyl radical pairs have lifetimes of up to ca. 4 ms and exclusively regenerate the starting ketone. We propose that these long lifetimes are the result of the short inter-radical distances and the colinear orientation of the two singly occupied orbitals, which are expected to result in large singlet–triplet energy gaps, large zero-field splitting parameters, and a poor geometry for spin-obit coupling. Ketones generating trityl–benzoyl radical pairs demonstrate promising performance along multiple dimensions that are crucial for quantum information science.

中文翻译：

在结晶三苯甲基酮中光化学产生的强缠结酰基-三苯甲基自由基对的超长寿命

最近引入了在其纳米晶酮前体的约束下由脉冲激光激发产生的三重态酰基-烷基自由基对，作为自旋量子位对在量子信息科学中应用的稳健和重复实例化的潜在平台。在这里，我们报告了一系列纳米晶三苯甲基-烷基和三苯甲基-芳基酮的瞬态光谱，这些酮能够产生相关的三重态自由基对，持久的三苯甲基自由基被迫保持在高反应性酰基自由基的键合距离内。三重态三苯甲基-酰基自由基对通过形成竞争产物的脱羰基和系统间交叉而衰变，而三重态三苯甲基-苯甲酰基自由基对的寿命长达 ca。4 毫秒，专门再生起始酮。我们认为这些长寿命是短的自由基间距离和两个单独占据的轨道的共线方向的结果，预计这将导致大的单重态-三重态能隙、大的零场分裂参数和较差的自旋比特耦合的几何学。产生三苯甲基-苯甲酰基自由基对的酮类在多个维度上表现出良好的性能，这对量子信息科学至关重要。

更新日期：2023-01-04

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