Extremely Stable Perylene Bisimide‐Bridged Regioisomeric Diradicals and Their Redox Properties

Feng, Zhibin; Zhou, Jiadong; He, Xiandong; Wang, Bohan; Xie, Guojing; Qiao, Xianfeng; Liu, Linlin; Xie, Zengqi; Ma, Yuguang

doi:10.1002/chem.202302943

“…Dieser Winkel ist dem des verwandten, vollständig chinoiden „Thiele“‐Diradikaloids (31°, Blasi) [7f] relativ ähnlich und unterscheidet sich deutlich von dem des „Müller“‐Diradikaloids (46°, Peng) [7e] sowie dem der Monoradikale TTM (51°) und PTM (47°) [11] . Der Trend zwischen den Diradikaloiden Thiele, Chichibabin und Müller lässt sich in erster Linie durch die zunehmend höheren energetischen Kosten erklären, die durch den Verlust der Aromatizität entstehen würden, wenn 1, 2 oder 3 Phenylenbrücken in ihrer chinoiden Form vorhanden sind, wie dies bei anderen Systemen beobachtet wurde [1b,3j,4c,d,p,7b,c,e,f,t,ae] . Für das „Chichibabin“‐Analogon TTM‐TTM bedeutet die zentrale Position in dieser Reihe, dass es Merkmale sowohl der chinoiden als auch der benzoiden Form gleichzeitig aufweist.…”

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Ein Stabiles Chichibabin Diradikaloid mit Nahinfraroter Emission

Chang,

Arnold,

Blinder

et al. 2024

Angewandte Chemie

0

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Conjugated molecules with multiple radical centers such as the iconic Chichibabin diradicaloid hold promise as building blocks in materials for quantum sensing and quantum information processing. However, it is a considerable challenge to design simple analogues of the Chichibabin hydrocarbon that are chemically inert, exhibit high diradical character and emit light at a distinct wavelength that may offer an optical readout of the spin state in functional ensembles. Here we describe the serendipitous discovery of the stable TTM‐TTM diradicaloid, which exhibits high diradical character, a striking sky‐blue color and near‐infrared (NIR) emission (in solution). This combination of properties is unique among related diradicaloids and is due to the presence of hydrogen and chlorine atoms in “just the right positions”, allowing a perfectly planar, yet predominantly benzenoid bridge to connect the two sterically stabilized radical centers. In‐depth studies of the optical and magnetic properties suggest that this structural motif could become a mainstay building block of organic spin materials.

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A Stable Chichibabin Diradicaloid with Near‐Infrared Emission

Chang,

Arnold,

Blinder

et al. 2024

Angew Chem Int Ed

6

0

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Conjugated molecules with multiple radical centers such as the iconic Chichibabin diradicaloid hold promise as building blocks in materials for quantum sensing and quantum information processing. However, it is a considerable challenge to design simple analogues of the Chichibabin hydrocarbon that are chemically inert, exhibit high diradical character and emit light at a distinct wavelength that may offer an optical readout of the spin state in functional ensembles. Here we describe the serendipitous discovery of the stable TTM‐TTM diradicaloid, which exhibits high diradical character, a striking sky‐blue color and near‐infrared (NIR) emission (in solution). This combination of properties is unique among related diradicaloids and is due to the presence of hydrogen and chlorine atoms in “just the right positions”, allowing a perfectly planar, yet predominantly benzenoid bridge to connect the two sterically stabilized radical centers. In‐depth studies of the optical and magnetic properties suggest that this structural motif could become a mainstay building block of organic spin materials.

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Perylene Bisimide‐Functionalized Triphenylmethyl Radicals Showing High Stability and Reversible Electrochemical Redox Properties

Feng,

Wang,

Zhou

et al. 2024

Chemistry A European J

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This study presents a series of triphenylmethyl monoradicals incorporating varying numbers of peripheral perylene bisimide (PBI) substituents (1PBI‐TTM·, 2PBI‐TTM· and 3PBI‐TTM·). The incorporation of electron‐withdrawing PBI substituents significantly enhances the stability of these carbon radicals, enabling them to display exceptional electrochemical redox reversibility. Notably, the electronic interplay between the PBI substituents and the central triphenylmethyl core facilitates unique and reversible multi‐step redox reactions. Among the reported redicals, the tris‐PBI functionalized radical (3PBI‐TTM·) demonstrates the remarkable ability to accommodate up to seven electrons under negative potentials, forming high valence anions. This research pioneers the development of highly stable carbon radicals with superior electrochemical oxidation‐reduction processes, presenting promising avenues for the advancement of electric energy storage technologies.

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Extremely Stable Perylene Bisimide‐Bridged Regioisomeric Diradicals and Their Redox Properties

Cited by 3 publications

References 85 publications

Ein Stabiles Chichibabin Diradikaloid mit Nahinfraroter Emission

Ein Stabiles Chichibabin Diradikaloid mit Nahinfraroter Emission

A Stable Chichibabin Diradicaloid with Near‐Infrared Emission

Perylene Bisimide‐Functionalized Triphenylmethyl Radicals Showing High Stability and Reversible Electrochemical Redox Properties

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