Relevant synthesis to manipulating non-planarity in dibenzo[g,p]chrysene: Substitution reactions at the bay

Kamiguchi, Shinsuke; Akasaka, Ryuhei; Yoshida, Naruhiro; Imai, Tomoya; Yamaoka, Yousuke; Amaya, Toru; Iwasawa, Tetsuo

doi:10.1016/j.tetlet.2022.153664

Cited by 5 publications

(8 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The longest absorption peak is attributed to the transition from HOMO to LUMO and HOMO-1 to LUMO+1 (see Tables S1-S6 in Supporting Information File 1). The trend for the order of optical band gap is roughly consistent with that of the HOMO-LUMO gap obtained from DFT calculation [52].…”

Section: Spectroscopic Propertiessupporting

confidence: 85%

“…Cyclic voltammograms (CVs) and square-wave voltammograms (SWVs) were measured for DBC-H, DBC-Me, DBC-SMe, DBC-Br, DBC-S(O) 2 Me, and DBC-Si (Figure 2) [53]. Table 1 summarizes the first and second oxidation potentials based on Fc/Fc + (E ox1 and E ox2 ) determined from the SWVs, together with the torsion angles determined from the X-ray crystal structures [52], the HOMO and LUMO levels determined from DFT calculations [52,54] and estimated based on E ox1 . The voltammogram of DBC-H exhibited a reversible, two-step, two-electron redox process, with E ox1 and E ox2 values of 0.34 V and 0.72 V, respectively (Figure 2a).…”

Section: Electrochemical Propertiesmentioning

confidence: 99%

“…We also recently reported on a synthetic strategy for preparing DBC derivatives using DBC-H with four isopropyl groups at X as a key template for the derivatization (Figure 1c). Based on this strategy, various substituents were introduced at Z to produce DBC-Br, DBC-Me, DBC-SMe, DBC-S(O) 2 Me, and DBC-Si (Figure 1c) [52]. The structures of all these derivatives were determined by X-ray crystallographic analysis, in which torsion angles were varied in a range from 31.8º (DBC-Si) to 57.4º (DBC-S(O) 2 Me) [52].…”

Section: Introductionmentioning

confidence: 99%

“…Based on this strategy, various substituents were introduced at Z to produce DBC-Br, DBC-Me, DBC-SMe, DBC-S(O) 2 Me, and DBC-Si (Figure 1c) [52]. The structures of all these derivatives were determined by X-ray crystallographic analysis, in which torsion angles were varied in a range from 31.8º (DBC-Si) to 57.4º (DBC-S(O) 2 Me) [52]. These DBC derivatives have four methoxy moieties at the Y position, which aroused our interest concerning the stability of those oxidation states.…”

Section: Introductionmentioning

confidence: 99%

“…SWVs were recorded at a platinum electrode at 298 K under Ar. b Based on Fc/Fc + .c The values obtained from X-ray crystallographic analyses[52].d The values obtained from DFT calculations at B3LYP6-31G(d,p)[52,54].e The energy values of HOMO were estimated based on the following equation E HOMO = −(E ox1 vs Fc+/Fc + 5.1)[55].…”

mentioning

confidence: 99%

See 4 more Smart Citations

Electrochemical and spectroscopic properties of twisted dibenzo[g,p]chrysene derivatives

Imai¹,

Akasaka²,

Yoshida³

et al. 2022

Beilstein J. Org. Chem.

Self Cite

View full text Add to dashboard Cite

Dibenzo[g,p]chrysene (DBC), which consists of a twisted naphthalene core with four fused benzene rings, is a promising framework for organic electronic materials. Therefore, the research for structure–property relationships is important for the design of DBC-based materials. Here, the electrochemical and spectroscopic properties of DBC derivatives were investigated, and the effects of substituents and torsion of the naphthalene moiety were examined based on density functional theory (DFT) calculations. All the substituted DBC derivatives showed higher oxidation potentials than that for DBC-H, even for compounds that contained an electron-donating group such as DBC-Me and DBC-SMe. DFT calculations clearly indicate that these higher oxidation potentials are due to the ineffective conjugation of the MeO group, which is oriented perpendicular to the benzene ring because of the steric repulsion of substituents on both sides. More specifically, the inductive effect of the MeO group is dominant rather than the mesomeric effect when the substituent is located at both sides of the MeO group. Concerning the torsion of the naphthalene moiety, the twisting results in a slight increase in the HOMO and a slight lowering of the LUMO. The twisting effect is much smaller than the conjugation effect of the MeO group. Absorption spectra of all the substituted DBC derivatives also showed a red-shift as compared to that for DBC-H. Concerning the luminescence, a strong photoluminescence was observed for DBC-H and DBC-Si.

show abstract

Section: Spectroscopic Propertiessupporting

confidence: 85%

Section: Electrochemical Propertiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

See 3 more Smart Citations

Electrochemical and spectroscopic properties of twisted dibenzo[g,p]chrysene derivatives

Imai¹,

Akasaka²,

Yoshida³

et al. 2022

Beilstein J. Org. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

Synthesis of an Octacyclic C₆₀ Fragment

et al. 2023

Self Cite

View full text Add to dashboard Cite

Fragments of buckminsterfullerene (C60) include the monumental three compounds corannulene, sumanene, and truxene. These three have served as leading molecules in ongoing research for curved, fused, and π‐extended polyaromatic materials. Achieving more structural variations that join the ranks of these three archetypes remains challenging. Herein we report synthesis of an octacyclic hydrocarbon that is an unexplored C60‐fragment, namely, a 4,11‐dihydrodiindeno[7,1,2‐ghi:7′,1′,2′‐pqr]chrysene (C28H16, which we named Metelykene). The key to success was solution‐compatible synthesis in which double pentagonal rings flank hexagonal ones. This solution‐phase approach, coupled with the resulting non‐planar π‐conjugation, is so straightforward that it offers an entry to a derivative such as a cardo aromatic monomer.

show abstract

Construction of Multiple Five‐Membered Rings in Dibenzo[g,p]chrysene Core for the Synthesis of a Nona‐Cycle Buckybowl

Yoshida,

Imai,

Amaya

et al. 2024

Eur J Org Chem

View full text Add to dashboard Cite

C60‐fragmentary bowl‐shaped molecules, commonly referred to as “buckybowls”, are provocative compounds, and their inviting functions based on the non‐planar π‐conjugation are expected. Yet, achieving synthesis of some kinds of the curved structure remaining challenging. Herein we report skeletal construction of a nona‐cyclic buckybowl that is synthetically unachievable heretofore, namely, 3,10‐dihydroindeno[7,1,2‐pqr]‐as‐indaceno[3,2,1,8,7‐defghi]chrysene. The key to success was solution‐compatible process in which a multiple substituted dibenzo[g,p]chrysene is amenable to threefold formation of five‐membered rings at its periphery. The resulting scheme here, coupled with the gently curved scaffold, offers a new insight into the solution‐phase synthesis of curved and twisted polyarenes.

show abstract

Relevant synthesis to manipulating non-planarity in dibenzo[g,p]chrysene: Substitution reactions at the bay

Cited by 5 publications

References 34 publications

Electrochemical and spectroscopic properties of twisted dibenzo[g,p]chrysene derivatives

Electrochemical and spectroscopic properties of twisted dibenzo[g,p]chrysene derivatives

Synthesis of an Octacyclic C₆₀ Fragment

Construction of Multiple Five‐Membered Rings in Dibenzo[g,p]chrysene Core for the Synthesis of a Nona‐Cycle Buckybowl

Contact Info

Product

Resources

About

Relevant synthesis to manipulating non-planarity in dibenzo[g,p]chrysene: Substitution reactions at the bay

Cited by 5 publications

References 34 publications

Electrochemical and spectroscopic properties of twisted dibenzo[g,p]chrysene derivatives

Electrochemical and spectroscopic properties of twisted dibenzo[g,p]chrysene derivatives

Synthesis of an Octacyclic C60 Fragment

Construction of Multiple Five‐Membered Rings in Dibenzo[g,p]chrysene Core for the Synthesis of a Nona‐Cycle Buckybowl

Contact Info

Product

Resources

About

Synthesis of an Octacyclic C₆₀ Fragment