Systematic Control of the Excited‐State Dynamics and Carrier‐Transport Properties of Functionalized Benzo[ghi]perylene and Coronene Derivatives

Abstract

A series of benzo[ghi]perylene (Bp) and coronene (Cor) derivatives substituted with electron-withdrawing methoxycarbonyl (COOMe) or electron-donating methoxyl (MeO) groups was synthesized. The electrochemical, spectroscopic, and photophysical properties of these compounds were investigated by cyclic voltammetry, steady-state and time-resolved spectroscopy, and quantum-yield measurements. Introduction of suitable substituents onto the aromatic rings enabled control of electrochemical and spectroscopic behavior. Examination of excited-state dynamics revealed that fluorescence quantum yields increased with increasing number of COOMe groups in both Bp and Cor derivatives, consistent with the findings of DFT calculations. Single-crystal analysis allowed the performance of field-effect transistors containing single crystals of the derivatives to be rationalized.

Synthesis and Electrochemical and Photophysical Properties of Azaterrylene Derivatives

“…The Φ FL value of MATerry (0.73) was slightly larger than that of Terry (0.66), while DiATerry (0.51) was smaller than that of Terry. The quantum yields of intersystem crossing pathways ( Φ ISC ) of azaterrylene derivatives were evaluated by measurements of singlet oxygen luminescence using energy transfer from the triplet excited states of the terrylene derivatives to O 2 . It should be noted that we assume that the quenching process of the excited singlet state by O 2 was negligible in these derivatives.…”

“…These molecules possess the characteristic optical and aggregate properties, which enables their promising applications in electronic and energy conversion devices . Among many π ‐conjugated molecules, pristine benzenoid PAHs are popular choices of p ‐type semiconductor materials . Moreover, heteroatom‐containing PAHs, such as nitrogen, sulfur and oxygen atoms, have received remarkable attentions due to the interesting spectroscopic and electrochemical properties as compared to the pristine PAHs.…”

Photoinduced Processes of Supramolecular Nanoarrays Composed of Porphyrin and Benzo[ghi]perylenetriimide Units through Triple Hydrogen Bonds with One‐Dimensional Columnar Phases

“…The measured half‐wave potentials ( E 1/2 ) of these compounds together with reference Bp are summarized in Table . The first one‐electron reduction potential ( E red1 ) of unsubstituted Bp was reported to be −2.20 V vs. SCE by our group . Similarly, the E red1 values of BpIm and Bp(Im) 3 were determined to be −1.33 and −0.66 V (vs. SCE), respectively (Figure S1 a and b).…”

“…Disk‐shaped polycyclic aromatic hydrocarbons (PAHs: e.g., perylene and benzo[ ghi ]perylene) with supramolecular columns formed by π ‐stacking interaction have been shown to demonstrate efficient one‐dimensional charge‐carrier transfer along the stacking axis . PAHs are generally popular choices of organic p‐type semiconductor materials with efficient UV/visible light absorption . However, introduction of electron‐accepting substituents (e.g., imide groups) onto the peripheral positions of a PAH ring enables us to control the electron acceptor behaviors .…”

Synthesis and photophysical properties of new reactive fluorophenanthrenes

“…The difference between the electrochemical and optical band gaps is attributed to the interface barrier between the electrode and each phenanthrene derivative [28,29] and the exciton binding energy. Interestingly, the energy band gap values of the tricyclic units P1-6 appear to be less than the electrochemical band gap (E g-el = 3.46 eV) of a benzo[ghi]perylene derivative bearing two electron-withdrawing methoxy carbonyl groups, which has been elaborated and used recently for the construction of field-effect transistors [30].…”