Allocation of Ambipolar Charges on an Organic Diradical with a Vinylene–Phenylenediyne Bridge

Burrezo, Paula Mayorga; Bejarano, Francesc; Calbo, Joaquín; Zhao, Xintong; Sousa, J. Alejandro de; Lloveras, Vega; Ortı́, Enrique; Veciana, Jaume; Rovira, Concepció; Crivillers, Núria

doi:10.1021/acs.jpclett.1c01565

Cited by 3 publications

(2 citation statements)

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“…PTM, [ 89 ] mPTM, [ 90 ] and bPTM [ 91 ] were synthesized and characterized as previously reported. Doped samples of mPTM in α H‐mPTM were obtained by solution mixing followed by drop casting.…”

Section: Methodsmentioning

confidence: 99%

Molecular One‐ and Two‐Qubit Systems with Very Long Coherence Times

Schäfter,

Wischnat,

Tesi

et al. 2023

Advanced Materials

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General‐purpose quantum computation and quantum simulation require multi‐qubit architectures with precisely defined, robust interqubit interactions, coupled with local addressability. This is an unsolved challenge, primarily due to scalability issues. These issues often derive from poor control over interqubit interactions. Molecular systems are promising materials for the realization of large‐scale quantum architectures, due to their high degree of positionability and the possibility to precisely tailor interqubit interactions. The simplest quantum architecture is the two‐qubit system, with which quantum gate operations can be implemented. To be viable, a two‐qubit system must possess long coherence times, the interqubit interaction must be well defined and the two qubits must also be addressable individually within the same quantum manipulation sequence. Here results are presented on the investigation of the spin dynamics of chlorinated triphenylmethyl organic radicals, in particular the perchlorotriphenylmethyl (PTM) radical, a mono‐functionalized PTM, and a biradical PTM dimer. Extraordinarily long ensemble coherence times up to 148 µs are found at all temperatures below 100 K. Two‐qubit and, importantly, individual qubit addressability in the biradical system are demonstrated. These results underline the potential of molecular materials for the development of quantum architectures.

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Section: Methodsmentioning

confidence: 99%

Molecular One‐ and Two‐Qubit Systems with Very Long Coherence Times

Schäfter,

Wischnat,

Tesi

et al. 2023

Advanced Materials

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“…107,108 Bis(phenylene)diyne bridges suppressed inter-radical interactions but, interestingly, PTM radicals proved effective in stabilising positive charges in the bridging units by forming quinoidal ring segments. 109 Electrochemical control of stable radical/radical, radical/anion and radical/cation pairs could perhaps be a versatile approach to obtain D–A radicals with switchable and strong optical responses.…”

Section: Carbon-centred π-Radicals Their Properties and Applicationsmentioning

confidence: 99%

Electro-optical π-radicals: design advances, applications and future perspectives

Murto

Bronstein

2022

J. Mater. Chem. C

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Unimolecular net heterolysis of symmetric and homopolar σ-bonds

Tiefel,

Grenda,

Allacher

et al. 2024

Nature

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The unimolecular heterolysis of covalent σ-bonds is integral to many chemical transformations, including SN1-, E1- and 1,2-migration reactions. To a first approximation, the unequal redistribution of electron density during bond heterolysis is governed by the difference in polarity of the two departing bonding partners1–3. This means that if a σ-bond consists of two identical groups (that is, symmetric σ-bonds), its unimolecular fission from the S0, S1, or T1 states only occurs homolytically after thermal or photochemical activation1–7. To force symmetric σ-bonds into heterolytic manifolds, co-activation by bimolecular noncovalent interactions is necessary4. These tactics are only applicable to σ-bond constituents susceptible to such polarizing effects, and often suffer from inefficient chemoselectivity in polyfunctional molecules. Here we report the net heterolysis of symmetric and homopolar σ-bonds (that is, those with similar electronegativity and equal leaving group ability3) by means of stimulated doublet–doublet electron transfer (SDET). As exemplified by Se–Se and C–Se σ-bonds, symmetric and homopolar bonds initially undergo thermal homolysis, followed by photochemically SDET, eventually leading to net heterolysis. Two key factors make this process feasible and synthetically valuable: (1) photoexcitation probably occurs in only one of the incipient radical pair members, thus leading to coincidental symmetry breaking8 and consequently net heterolysis even of symmetric σ-bonds. (2) If non-identical radicals are formed, each radical may be excited at different wavelengths, thus rendering the net heterolysis highly chemospecific and orthogonal to conventional heterolyses. This feature is demonstrated in a series of atypical SN1 reactions, in which selenides show SDET-induced nucleofugalities3 rivalling those of more electronegative halides or diazoniums.

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Allocation of Ambipolar Charges on an Organic Diradical with a Vinylene–Phenylenediyne Bridge

Cited by 3 publications

References 40 publications

Molecular One‐ and Two‐Qubit Systems with Very Long Coherence Times

Molecular One‐ and Two‐Qubit Systems with Very Long Coherence Times

Electro-optical π-radicals: design advances, applications and future perspectives

Unimolecular net heterolysis of symmetric and homopolar σ-bonds

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