Photophysical property, electronic structure and solid-state packing of O-heterocyclic annulated perylene diimide

Abstract

Purpose Self-organization has been regarded as a tool for the synthesis of well-defined organic nanostructures. Heterocyclic annulated perylene diimides are the subjects of considerable current research studies. The purpose of this study is to reveal the photophysical property, electronic structure and solid-state packing of O-heterocyclic annulated perylene diimide. Design/methodology/approach Asymmetrically five-membered O-heterocyclic annulated perylene diimide (OAPDI) was synthesized. Structure and purity of OAPDI were confirmed by 1H NMR, 13C NMR, IR and mass spectral techniques. Photophysical properties of OAPDI were studied using UV–vis absorption and fluorescence in both solution (CHCl3) and solid state. Scanning electron microscopic and atomic force microscopy were used to characterize the surface morphology of OAPDI. Conducting properties of the OAPDI were evaluated by current–voltage measurements. The compounds geometries were also optimized at 6-31G* using density functional theory. Findings The UV–vis absorption and fluorescence spectra of OAPDI in solution are blue-shifted in comparison with that of unsubstituted perylene bisimide. Solid-state UV–vis measurements of OAPDI indicate that it is capable of forming highly ordered structure. The non-covalent interactions, electrostatic attraction and p-p stacking moieties of OAPDI synergistically guide assembly and domain growth while maintaining the interpenetrating network of nanofibers in the solid film. The OAPDI gave higher current at −2.0 V (0.68 µA) and 4.0 V (1.0 µA). Originality/value This study will be helpful for exploring feasible routes to acquire soluble perylene diimides and well-defined organic nanostructures. Furthermore, such molecular tailoring approach would be helpful for designing and synthesizing novel organic semiconductive materials with excellent charge-transporting and light-emitting capabilities.

Ultrafast Intersystem Crossing in Selenium-Annulated Perylene Bisimide

“…We have synthesized chalcogenide PBIs ( O-PBI , S-PBI , and Se-PBI ) according to the previously reported procedures − (Scheme S1) and characterized using analytical and spectroscopic techniques (Figure ). Geometry optimization of O-PBI , S-PBI , and Se-PBI using the DFT (B3LYP/def2-SVP) level of theory suggests an increase in the C–X bond length and a decrease in the C–X–C bond angle as we move from O-PBI to Se-PBI (Figure S1).…”

Recent Advances in Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds

“…Bay-nitrated PDI 60.1a was converted into the O-annulated derivative 60.2 in 30% yield by heating in NMP under an oxygen atmosphere. 104 , 105 Additionally, the S - annulated analogue 60.3 was prepared using a similar methodology. 104 , 106 Spectroscopic and electrochemical data of this compound were reported and compared with several nonannulated analogues.…”

“…As an alternative to the synthetic sequence shown in Scheme , the heteroatom annulation can be done after diimide formation (Scheme ). Bay-nitrated PDI 60.1a was converted into the O-annulated derivative 60.2 in 30% yield by heating in NMP under an oxygen atmosphere. , Additionally, the S - annulated analogue 60.3 was prepared using a similar methodology. , Spectroscopic and electrochemical data of this compound were reported and compared with several nonannulated analogues . The O - annulated compound 60.2 displayed slightly red-shifted absorption and emission (λ abs = 510 nm, λ em = 522 nm) in comparison to 60.3 (λ abs = 500 nm, λ em = 515 nm).…”

“… a Reagents and conditions: (a) , NMP, O 2 , 180 °C, 5 h, 30%; (b) sulfur powder, NMP, 130 °C, 12 h, 32%; (c) sulfur powder, NMP, 70 °C then 60.1b , 190 °C, 3 h, 52%; (d) selenium powder, NMP, 70 °C then 60.1b , 190 °C, 3 h, 48%. …”