Heteroatom Cycloaddition at the (BN)<sub>2</sub>Bay Region of Dibenzoperylene

Fingerle, Michael; Dingerkus, Juliane; Schubert, Hartmut; Wurst, Κ.; Scheele, Marcus; Bettinger, Holger F.

doi:10.1002/anie.202016699

Cited by 10 publications

(1 citation statement)

References 69 publications

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“…Boron atom with an empty p‐orbital is a special electron‐deficient heteroatom. Doping boron atoms into PHs has afforded a large number of B‐doped PHs, which not only have intriguing chemical structures but also are promising organic semiconductors, light‐emitting materials and catalysts [26–41] . However, B‐containing diradical PHs are very challenging, because they suffer from high reactivities due to diradical nature and boron atom [42–45] .…”

Section: Introductionmentioning

confidence: 99%

Tuning Diradical Properties of Boron‐Containing π‐Systems by Structural Isomerism

Tian

Guo

Sun

et al. 2022

Chemistry A European J

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Tuning diradical character is an important topic for organic diradicaloids. Herein, we report the precise borylation enabling structural isomerism as an effective strategy to modulate diradical character and thereby properties of organic diradicaloids. We synthesized a new B‐containing polycyclic hydrocarbon that has the indeno[1,2‐b]fluorene π‐skeleton with the β‐carbons bonding to two boron atoms. Detailed theoretical and experimental results show that this bonding pattern leads to its distinctive electronic structures and properties in comparison to that of its isomeric molecule. This molecule has the efficient conjugation between boron atoms and π‐skeleton, resulting in downshifted LUMO and HOMO levels. Moreover, it exhibits smaller diradical character and thereby inhibited diradical properties, such as significantly blue‐shifted light absorption, larger energy bandgap and weak para‐magnetic resonance. Notably, this B‐containing polycyclic hydrocarbon possesses much stronger Lewis acidity and its Lewis acid‐base adducts display enhanced diradical character, demonstrating the positive effects of Lewis coordination on modulating diradical performance.

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Section: Introductionmentioning

confidence: 99%

Tuning Diradical Properties of Boron‐Containing π‐Systems by Structural Isomerism

Tian

Guo

Sun

et al. 2022

Chemistry A European J

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Regioregular Poly(p‐phenylene iminoborane): A Strictly Alternating BN‐Isostere of Poly(p‐phenylene vinylene) with Stimuli‐Responsive Behavior

Chorbacher,

Klopf,

Friedrich

et al. 2024

Angewandte Chemie

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Incorporation of BN units into π‐conjugated organic compounds, as substitutes for specific CC couples, often leads to new hybrid materials with modified physical and chemical properties. Poly(p‐phenylene iminoborane)s are derived from well‐known poly(p‐phenylene vinylene) (PPV) by replacement of the vinylene groups by B=N linking units. Herein, an unprecedented poly(p‐phenylene iminoborane) is presented that features a strictly alternating sequence of BN units along the main chain. The synthesis thereof was achieved by AB‐type polymerization of a monomer featuring an N and a B terminus. Monodisperse oligomers with up to three BN units in the chain were additionally prepared and structurally characterized. Associated with the introduction of a dipole in the regioregular backbone structure, they display notable fluorescence already in solution and large Stokes shifts, distinct from their previously reported BBNN‐sequenced congeners. All compounds show aggregation‐induced emission enhancement (AIEE) properties. Computational studies provided evidence for emission from either locally excited (LE) or twisted intramolecular charge transfer (TICT) states. These processes can be optionally addressed by various stimuli, giving rise to dual emission, solvatochromic, thermochromic, and reversible mechanochromic behavior.

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Fluorescence Modulation through the Inverted Energy Gap Law in Triply N−B←N‐Containing Windmill‐Shaped Triazines

Feng,

Wang,

Gao

et al. 2024

Angewandte Chemie

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A series of windmill‐shape heterocyclic molecules containing three N─B←N units, TBN and its derivatives, with quasi‐planar C3 symmetric backbone, are synthesized. The parent TBN exhibits a strongly allowed, doubly degenerate lowest excited state but suffers from very low fluorescence, due to very fast nonradiative decay rate through a conical intersection (CI) as revealed by femtosecond transient absorption spectroscopy and quantum‐chemical calculations. Introducing peripheral phenyl‐ or thienyl‐groups (Ph‐TBN or Th‐TBN) induces pronounced bathochromic shifts and enhances fluorescence, which is beneficial from inhibited nonradiative pathway by the increased energy barriers to access the CI at excited state. The understanding of this rather uncommon behaviour may open routes for the design of novel fluorescence materials.

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Heteroatom Cycloaddition at the (BN)₂Bay Region of Dibenzoperylene

Cited by 10 publications

References 69 publications

Tuning Diradical Properties of Boron‐Containing π‐Systems by Structural Isomerism

Tuning Diradical Properties of Boron‐Containing π‐Systems by Structural Isomerism

Regioregular Poly(p‐phenylene iminoborane): A Strictly Alternating BN‐Isostere of Poly(p‐phenylene vinylene) with Stimuli‐Responsive Behavior

Fluorescence Modulation through the Inverted Energy Gap Law in Triply N−B←N‐Containing Windmill‐Shaped Triazines

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Heteroatom Cycloaddition at the (BN)2Bay Region of Dibenzoperylene

Cited by 10 publications

References 69 publications

Tuning Diradical Properties of Boron‐Containing π‐Systems by Structural Isomerism

Tuning Diradical Properties of Boron‐Containing π‐Systems by Structural Isomerism

Regioregular Poly(p‐phenylene iminoborane): A Strictly Alternating BN‐Isostere of Poly(p‐phenylene vinylene) with Stimuli‐Responsive Behavior

Fluorescence Modulation through the Inverted Energy Gap Law in Triply N−B←N‐Containing Windmill‐Shaped Triazines

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Heteroatom Cycloaddition at the (BN)₂Bay Region of Dibenzoperylene