Understanding the mechanism of singlet exciton fission, in which a singlet exciton separates into a pair of triplet excitons, is crucial to the development of new chromophores for efficient fission-sensitized solar cells. The challenge of controlling molecular packing and energy levels in the solid state precludes clear determination of the singlet fission pathway. Here, we circumvent this difficulty by utilizing covalent dimers of pentacene with two types of side groups. We report rapid and efficient intramolecular singlet fission in both molecules, in one case via a virtual charge-transfer state and in the other via a distinct charge-transfer intermediate. The singlet fission pathway is governed by the energy gap between singlet and charge-transfer states, which change dynamically with molecular geometry but are primarily set by the side group. These results clearly establish the role of charge-transfer states in singlet fission and highlight the importance of solubilizing groups to optimize excited-state photophysics.
Synthesis of a carbon nanobelt (CNB) is a very challenging task in organic chemistry. Herein, we report the successful synthesis of an octabenzo[12]cyclacene based CNB (6), which can be regarded as a sidewall fragment of a (12,0) carbon nanotube. The key intermediate compound, a tetraepoxy nanobelt (5), was first synthesized by Diels–Alder reaction, and subsequent reductive aromatization gave the fully conjugated CNB 6. X‐ray crystallographic analysis unambiguously confirmed the belt‐shaped structure of 6. 1H NMR spectrum and theoretical calculations (ACID, NICS, and 2D/3D ICSS) revealed localized aromaticity and stronger shielding chemical environment in the inner region of the belt. The optical properties (absorption and emission) of 6 were studied and correlated to its electronic structure. Strain analysis indicates that the phenyl substituents at the zigzag edges are crucial to the successful synthesis of 6. This report presents a new strategy towards highly strained CNBs.
Higher order acenes (i.e., acenes longer than pentacene) and extended zethrenes (i.e., zethrenes longer than zethrene) are theoretically predicted to have an open-shell singlet ground state, and the radical character is supposed to increase with extension of molecular size. The increasing radical character makes the synthesis of long zethrenes and acenes very challenging, and so far, the longest reported zethrene and acene derivatives are octazethrene and nonacene, respectively. In addition, there is a lack of fundamental understanding of the differences between these two closely related open-shell singlet systems. In this work, we report the first synthesis of a challenging nonazethrene derivative, HR-NZ, and its full structural and physical characterizations including variable temperature NMR, ESR, SQUID, UV-vis-NIR absorption and electrochemical measurements. Compound HR-NZ has an open-shell singlet ground state with a moderate diradical character (y0 = 0.48 based on UCAM-B3LYP calculation) and a small singlet-triplet gap (ΔES-T = -5.2 kcal/mol based on SQUID data), thus showing magnetic activity at room temperature. It also shows amphoteric redox behavior, with a small electrochemical energy gap (1.33 eV). Its electronic structure and physical properties are compared with those of Anthony's nonacene derivative JA-NA and other zethrene derivatives. A more general comparison between higher order acenes and extended zethrenes was also conducted on the basis of ab initio electronic structure calculations, and it was found that zethrenes and acenes have very different spatial localization of the unpaired electrons. As a result, a faster decrease of singlet-triplet energy gap and a faster increase of radical character with increase of the number of benzenoid rings were observed in zethrene series. Our studies reveal that spatial localization of the frontier molecular orbitals play a very important role on the nature of radical character as well as the excitation energy.
Incorporation of anon-hexagonal ring into ananographene framework can lead to new electronic properties. During the attempted synthesis of naphthalene-bridged double [6]helicene and heptagon-containing nanographene by the Scholl reaction, an unexpected azulene-embedded nanographene and its triflyloxylated product were obtained, as confirmed by X-rayc rystallographic analysis and 2D NMR spectroscopy. A5/7/7/5 ring-fused substructure containing two formal azulene units is formed, but only one of them shows an azulene-like electronic structure.The formation of this unique structure is explained by arenium ion mediated 1,2-phenyl migration and an aphthalene to azulene rearrangement reaction according to an in-silico study.This report represents the first experimental example of the thermodynamically unfavorable naphthalene to azulene rearrangement and may lead to new azulene-based molecular materials.
Two series of oligothiophenes (OThs), NaTn and TNTn (n = 2–6 represents the number of thiophene rings), end‐capped with naphthyl and thionaphthyl units have been synthesized by means of Stille coupling. Their thermal properties, optical properties, single crystal structures, and organic field‐effect transistor performance have been characterized. All oligomers display great thermal stability and crystallinity. The crystallographic structures of NaT2, NaT3, TNT2, and TNT3 have been determined. The crystals of NaT2 and NaT3 are monoclinic with space group P21/C, while those of TNT2 and TNT3 are triclinic and orthorhombic with space groups P and P212121, respectively. All oligomers adopt the well‐known herringbone packing‐mode in crystals with packing parameters dependent on the structure of the end‐capping units and the number of thiophene rings. The shorter intermolecular distance in NaT3 compared to NaT2 indicates that the intermolecular interaction principally increases with increasing molecular length. X‐ray diffraction and atomic force microscopy (AFM) characterization indicate that the NaTn oligomers can form films with better morphology and high molecular order than TNTn oligomers with the same number of thiophene rings. The NaTn oligomers exhibit mobilities that are much higher than those for TNTn oligomers (0.028–0.39 cm2 V–1 s–1 versus 0.010–0.055 cm2 V–1 s–1, respectively). In particular, the NaTn oligomers with n = 4–6 all show a mobility higher than 0.1 cm2 V–1 s–1. This device performance is among the best in aryl end‐capped OThs, and indicates that naphthyl is an effectual building block for designing high‐performance organic semiconducting materials.
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