Synthesis, structural analysis, and properties of highly twisted alkenes 13,13’-bis(dibenzo[a,i]fluorenylidene) and its derivatives

Kang, Hao-Wen; Liu, Yu-Chiao; Shao, Wei-Kai; Wei, Yu-Chen; Hsieh, Chi-Tien; Chen, Bo-Han; Lu, Chih-Hsuan; Yang, Shang-Da; Cheng, Mu-Jeng; Chou, Pi-Tai; Chiang, Ming-Hsi; Wu, Yao-Ting

doi:10.1038/s41467-023-40990-8

Cited by 7 publications

(2 citation statements)

References 51 publications

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“…The inspired structural modification may lead to a plethora of switching molecules in the future . The authors hope that this review will help accelerate the development of interesting organic compounds in this category.…”

Section: Discussionmentioning

confidence: 99%

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Carbon-based Biradicals: Structural and Magnetic Switching

Ishigaki,

Harimoto,

Shimajiri

et al. 2023

Chem. Rev.

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Sterically hindered C�C double bonds often deform into a bent or twisted geometry. Thus, many overcrowded ethylenes or anthraquinodimethanes can adopt multiple conformations, such as a folded form or a twisted form, which are interconvertible under the application of external stimuli. A perpendicular form with biradical character can also be adopted when designed to incorporate a stable carbon-based radical unit, which is involved in stimuliresponsive magnetic switching accompanied by a structural change. This review focuses on recent advances in the development of such strained π-electron systems and reveals the factors that affect the mutual interconversion and switching behavior. The energy barrier for the interconversion of conformational isomers is affected by the tricyclic skeleton or bulky substituents on the C�C double bonds, whereas the relative stability of the perpendicular biradical form increases with the additional insertion of 9,10-anthrylene units into the C�C double bonds. CONTENTS 1. Introduction 13952 2. Difference between the Open-shell Perpendicular Form and the Closed-shell Twisted Form 13953 3. Interconversion between the Biradical Perpendicular Form and Closed-shell Twisted Form of Overcrowded Ethylene 13955 4. Interconversion between the Biradical Perpendicular Form and Closed-shell Folded Form of Anthraquinodimethanes 13956 5. Biradical Perpendicular Form Derived from the Closed-shell Folded Form of Bianthraquinodimethanes 13958 6. Stable Biradical Perpendicular Form with an Oligo(9,10-anthrylene) Unit 13960 7. Biradical Perpendicular Form

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Section: Discussionmentioning

confidence: 99%

“…The inspired structural modification may lead to a plethora of switching molecules in the future. 125 The authors hope that…”

Section: Discussionmentioning

confidence: 99%

Carbon-based Biradicals: Structural and Magnetic Switching

Ishigaki,

Harimoto,

Shimajiri

et al. 2023

Chem. Rev.

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Ein Stabiles Chichibabin Diradikaloid mit Nahinfraroter Emission

Chang,

Arnold,

Blinder

et al. 2024

Angewandte Chemie

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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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Azadihomocorannulene as a Heptagon‐Embedded Diradicaloid

Hamamoto,

Wang,

et al. 2024

Angewandte Chemie

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Polycyclic aromatic diradical(oid) molecules are attracting significant attention because of their unique electronic and magnetic properties as well as their applications as functional materials. While diradical(oid) molecules bearing five‐membered rings have been extensively investigated, those bearing seven‐membered rings are relatively fewer. Herein, we report the synthesis of azapentabenzodihomocorannulene dication and diradical molecules. The synthesis was achieved through a mechanochemical C(sp2)–H/C(sp3)–H coupling in the presence of sodium as a key reaction. Electron spin resonance studies revealed that the neutral azapentabenzodihomocorannulene adopts a singlet diradical (diradicaloid) ground state with a small singlet–triplet energy gap of 2.1 kcal/mol. The electronic and optical properties were investigated both experimentally and theoretically to elucidate their aromatic character.

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Synthesis, structural analysis, and properties of highly twisted alkenes 13,13’-bis(dibenzo[a,i]fluorenylidene) and its derivatives

Cited by 7 publications

References 51 publications

Carbon-based Biradicals: Structural and Magnetic Switching

Carbon-based Biradicals: Structural and Magnetic Switching

Ein Stabiles Chichibabin Diradikaloid mit Nahinfraroter Emission

Azadihomocorannulene as a Heptagon‐Embedded Diradicaloid

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