Synthesis, Structure and Solid State Properties of Cyclohexanemethylamine Substituted Phenalenyl Based Molecular Conductor

Phenalenyl derivatives have been of tremendous interest due to their reversible dimerization in response to the external stimuli such as temperature. However, most of PLY derivatives only show the reversibility dependent on temperature. Herein, we report a unique PLY-based radical anionic salt with reversible σ-dimerization controlled by solvent rather than temperature. The structure and reversibility of this PLY anion system have been spectroscopically, crystallographically, and theoretically investigated. The molecule exists mainly as the σ-dimer form of K2 [σ-12] in toluene, while it can be broken into the monomeric radical anion 1 •by re-dissolving in THF. Moreover, when THF is replaced with toluene, radical 1 •could be σ-dimerized back again. Theoretical calculations reveal that the potassium ions are necessary for the formation of the σ-dimer and the solvent polarity controls the σ-dimerization by regulating the presence of K + .

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Room‐Temperature Reversible σ‐Dimerization of a Phenalenyl Radical

Dong

Sun

Feng

et al. 2022

Chin. J. Chem.

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Bidirectional non-innocence of the β-diketonato ligand 9-oxidophenalenone (L−) in [Ru([9]aneS3)(L)(dmso)]n, [9]aneS3 = 1,4,7-trithiacyclononane

et al. 2014

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The new compound [Ru(II)([9]aneS3)(L)(dmso)]ClO4 ([]ClO4) ([9]aneS3 = 1,4,7-trithiacyclononane, HL = 9-hydroxyphenalenone, dmso = dimethylsulfoxide) has been structurally characterised to reveal almost equal C-O bond distances of coordinated L(-), suggesting a delocalised bonding situation of the β-diketonato ligand. The dmso ligand is coordinated via the sulfur atom in the native (1+) and reduced states (1 and 1-) as has been revealed by X-ray crystallography and by DFT calculations. Cyclic voltammetry of 1+ exhibits two close-lying one-electron oxidation waves at 0.77 V and 0.94 V, and two similarly close one-electron reduction processes at -1.43 V and -1.56 V versus SCE in CH2Cl2. The electronic structures of 1n in the accessible redox states have been analysed via experiments (EPR and UV-vis-NIR spectroelectrochemistry) and by DFT/TD-DFT calculations, revealing the potential for bidirectional non-innocent behaviour of coordinated L(˙/-/˙2-). Specifically, the studies establish significant involvement of L based frontier orbitals in both the oxidation and reduction processes: [([9]aneS3)(dmso)Ru(III)-L˙](3+) (1(3+)) ⇌ [([9]aneS3)(dmso)Ru(III)-L(-)](2+)/[([9]aneS3)(dmso)Ru(II)-L˙](2+) (1(2+)) ⇌ [([9]aneS3)(dmso)Ru(II)-L(-)](+) (1(+)) ⇌ [([9]aneS3)(dmso)Ru(II)-L(˙2-)] (1) ⇌ [([9]aneS3)(dmso)Ru(II)-L(3-)](-)/[([9]aneS3)(dmso)Ru(I)-L(˙2-)](-) (1-).

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Trioxotriangulene: Air- and Thermally Stable Organic Carbon-Centered Neutral π-Radical without Steric Protection

Morita

Murata

Ueda

et al. 2018

Bulletin of the Chemical Society of Japan

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To stabilize organic neutral radicals, which are usually very unstable chemical species in air atmosphere, “steric protection” is the most general and indispensable method. Based on the design of electronic-spin structure of polycyclic carbon-centered π-radicals, we have for the first time realized a peculiarly stable neutral π-radical without bulky substituent groups, 4,8,12-trioxotriangulene (TOT), whose decomposition point is higher than 240 °C in the solid state under air. This remarkably high air-stability as a neutral radical is achieved by spin-delocalization originating from the symmetric and expanded π-electronic structure of TOT. The oxo-functionalities also highly contribute to the high stability through electronic-spin modulation, where the largest electronic spin density located at the central carbon atom further decreases the spin densities of the peripheral carbon atoms. In the solution state, TOT is in the equilibrium between the monomer and highly symmetric π-dimer, as stabilized by the formation of the strong two-electron-multicenter bonding. Crystal structure analysis revealed that TOT derivatives show strong self-assembling ability forming one-dimensional columns, which further construct three-dimensional networks by multiple intercolumnar non-covalent interactions due to the absence of bulky substituent groups. Substituent groups at the apexes of the triangular carbon-framework of TOT afford variations of the π-stacking mode in the one-dimensional columns, influencing the magnetic properties and photo-absorptions around the near-infrared region. The electronic effect of the substituent groups also affects the redox potentials of TOT. The peculiarly high stability of TOT neutral radicals and their three-dimensional networks by robust intermolecular interactions achieved in our study are very beneficial for the molecular design of new polycyclic air-stable neutral radicals. Furthermore, we believe that the open-shell electronic structures of neutral π-radicals, which are quite different from those of close-shell molecular systems, will also produce milestones for the exploration of peculiar physical properties and catalytic activity for organic transformation originating from their unconventional electronic-spin nature.

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Synthesis, Structure and Solid State Properties of Cyclohexanemethylamine Substituted Phenalenyl Based Molecular Conductor

Cited by 4 publications

References 67 publications

Room‐Temperature Reversible σ‐Dimerization of a Phenalenyl Radical

Room‐Temperature Reversible σ‐Dimerization of a Phenalenyl Radical

Bidirectional non-innocence of the β-diketonato ligand 9-oxidophenalenone (L−) in [Ru([9]aneS3)(L)(dmso)]n, [9]aneS3 = 1,4,7-trithiacyclononane

Trioxotriangulene: Air- and Thermally Stable Organic Carbon-Centered Neutral π-Radical without Steric Protection

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