π-Pimer, π-Dimer, π-Trimer, and 1D π-Stacks in a Series of Benzene Triimide Radical Anions: Substituent-Modulated π Interactions and Physical Properties in Crystalline State

Tuo, De‐Hui; Tang, Shuxuan; Jin, Pengfei; Li, Jikun; Wang, Xinping; Zhang, Chuang; Ao, Yu‐Fei; Wang, Qi‐Qiang; Wang, De‐Xian

doi:10.31635/ccschem.022.202202167

Cited by 10 publications

(9 citation statements)

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“…In addition, the shortest C···C interaction between two adjacent TCNQF 4 molecules is 3.217 Å, which was far longer than a typical sp 3 –sp 3 bond (1.54 Å) but substantially shorter than the sum of van der Waals radii of two sp 2 carbon atoms (∼3.4 Å). Such close π-stacking distances between the TCNQF 4 molecules indicate the formation of dimeric π-associations driven by a large SOMO–SOMO overlap between two TCNQF 4 anion radicals . On this account, the TCNQF 4 molecules might be regarded as a 1D infinite stack consisting of the π-dimers of TCNQF 4 moieties within the crystal lattice.…”

Section: Resultsmentioning

confidence: 99%

“…Such close π-stacking distances between the TCNQF 4 molecules indicate the formation of dimeric π-associations driven by a large SOMO−SOMO overlap between two TCNQF 4 anion radicals. 53 On this account, the TCNQF 4 molecules might be regarded as a 1D infinite stack consisting of the π-dimers of TCNQF 4 moieties within the crystal lattice. Between the adjacent π-dimers, despite a relatively short interplane distance of 3.005 Å found from the side view, the top view shows that marginal overlaps that connected through intermolecular (cyano)N•••(phenyl)C and (phenyl)F••• (cyano)C noncovalent interactions were found between the TCNQF 4 dimers (Figure 3B), thus leading to the formation of a typical slipped 1D column of the TCNQF 4 π-dimers.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Magnetic Bistability in an Organic Radical-Based Charge Transfer Cocrystal

Lai,

Bu,

Xiao

et al. 2023

J. Am. Chem. Soc.

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We report herein an organic charge transfer cocrystal complex, consisting of a stable radical TPVr and an electron acceptor TCNQF 4 , as a rare sort of all-organic-based magnetic bistable materials with a thermally activated magnetic hysteresis loop over the temperature range from 170 to 260 K. Detailed X-ray crystallographic studies and theoretical calculations revealed that while a π-associated radical anion dimer was formed upon an integer charge transfer process from TPVr to the TCNQF 4 molecules within the cocrystal lattice, the resulting TCNQF 4 ·– π-dimers were found to exhibit varied intradimer π-stacking distances and singly occupied molecular orbital overlaps at different temperatures, thus yielding two different singlet states with distinct singlet–triplet gaps above and below the loop, which eventually contributed to the thermally excited molecular magnetic bistability.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Magnetic Bistability in an Organic Radical-Based Charge Transfer Cocrystal

Lai,

Bu,

Xiao

et al. 2023

J. Am. Chem. Soc.

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“…Since building blocks of π-stacking manner with infinite stacking would be effective for conductivity, the conductivity measurements on [BN-Cor1] 3 **2 + and [BN-Cor2] 3 **2 + were carried out on the pressed powder pellet at ambient temperature using a two probe method and the results are listed in Table S20 and Table S21 **2 + at 3 MPa were 3.44×10 À 5 S cm À 1 and 2.48×10 À 5 S cm À 1 , respectively, which is comparable to the benzene triimide radical pimers with infinite layered configuration. [25] The conductivity property of the radical trimers could be attributed to the charge hopping between the stacking skeletons.…”

Section: Methodsmentioning

confidence: 99%

Mixed‐Valence BN‐Doped Corannulene Trimer Radical Cations

Gao,

Liu,

et al. 2023

Angew Chem Int Ed

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Mixed‐valence (MV) dimers have been extensively investigated, however, the structures and properties of purely organic MV trimers based on open‐shell polycyclic aromatic hydrocarbons remain elusive. Herein, unprecedented MV BN‐doped corannulene radical cations [BN‐Cor1]3••2+•2[BArylF4]‐ and [BN‐Cor2]3••2+•2[BArylF4]‐ were synthesized via chemical oxidation, and their structures were unambiguously confirmed by single‐crystal X‐ray diffraction. These uncommon radical cations consist of three corannulene cores and two [BArylF4]‐ anions, and three corannulene motifs [BN‐Cor1]3••2+ and [BN‐Cor2]3••2+ in the unit cell exhibit a trimer structure with a slipped π‐stacking configuration. Detailed structural analyses further revealed that the corannulene cores exhibit an infinite layered self‐assembly configuration, allowing their potential applications as building blocks for molecular conductors. The detection of forbidden transition (Δms = ± 2) by electron paramagnetic resonance (EPR) spectroscopy further confirmed the existence of two unpaired electrons in the π‐trimers and the MV characteristic of these two species. Variable‐temperature EPR and conductivity measurements suggested that the BN‐doped π‐trimers exhibited antiferromagnetic coupling and conductivity properties

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“…[32][33][34] BTIs can be transformed into radical anions by chemical reduction, representing a new type of stable radicals showing unique magnetic property and conductivity. [35][36][37] The peculiar stability of BTI-radicals (bulky protecting groups are not necessary) was accounted for by the delocalization of spin over the aromatic backbone and the absence of reactive carbon center. Our previous study indicated that BTI radicals show distinct NIR absorption which was ascribed to the transition between singly occupied molecular orbital (SOMO) of the unpaired electron spin and LUMO + 1 orbital.…”

Section: Introductionmentioning

confidence: 99%

“…Our previous study indicated that BTI radicals show distinct NIR absorption which was ascribed to the transition between singly occupied molecular orbital (SOMO) of the unpaired electron spin and LUMO + 1 orbital. [36,37] We envisioned BTI could be a good molecular platform to construct stable chiral radicals. As chiral groups bearing various α-substituents could be readily introduced on the three nitrogen atoms, [32] different interplay of the unpaired electron spin and chirality is anticipated to be modulated (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Chiral Benzene Triimide (BTI) Radical Anions for Probing the Interplay of Unpaired Electron Spin and Chirality

Tuo,

Ao,

Wang

et al. 2023

Chemistry A European J

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Herein a series of chiral BTI radical anions bearing different chiral substituents were efficiently prepared by chemical reduction. X‐ray crystallography revealed finely‐tuned packing and helix assemblies of the radicals by the size of chiral substituents in crystalline state. In accordance with the crystalline‐state packing, the powder ESR spectra indicate that 4a–•CoCp2+ and 4c–•CoCp2+ π‐dimers exhibit thermally excited triplet states arising from strong spin‐spin interactions, while discrete 4b–•CoCp2+ shows a broad doublet‐state signal reflecting to weak spin‐spin interactions. The interplay between the unpaired electron spin and chiral substituents was studied by UV‐Vis‐NIR spectra, electronic circular dichroism (ECD) and TD DFT calculations. Different NIR absorptions of the radicals attributing to isolated SOMO→LUMO+1 (~889 nm) transitions were recorded. The emergence of Cotton effects (CEs) at the NIR region for 4c–•CoCp2+ radical enantiomers suggest the interplay between chirality and unpaired electron spin. The origin of the different circularly polarized light absorptions regarding SOMO derived transitions (around 880 nm) was attributed to chiral substitutes regulated electric and magnetic transition dipole moments of the unpaired electron participated transition.

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π-Pimer, π-Dimer, π-Trimer, and 1D π-Stacks in a Series of Benzene Triimide Radical Anions: Substituent-Modulated π Interactions and Physical Properties in Crystalline State

Cited by 10 publications

References 0 publications

Magnetic Bistability in an Organic Radical-Based Charge Transfer Cocrystal

Magnetic Bistability in an Organic Radical-Based Charge Transfer Cocrystal

Mixed‐Valence BN‐Doped Corannulene Trimer Radical Cations

Chiral Benzene Triimide (BTI) Radical Anions for Probing the Interplay of Unpaired Electron Spin and Chirality

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