Enhanced Intramolecular Charge Transfer in New Type Donor–Acceptor Substituted Perylenes

Abstract

Here we report the facile synthesis and physical characterization of new type N-(2,6-diisopropylphenyl)-3,4-perylenedicarboximides (PMI) with alkyl-substituted quinoline-4(1H)-ylidenemethyl or acridine-9(10H)-ylidenemethyl units as strong donors in the 9-position. When compared to parent PMI, these perylene dyes, 9-((1-methylquinoline-4(1H)-ylidene)methyl)-PMI, 9-((1-benzylquinoline-4(1H)ylidene)methyl)-PMI, 9-((1-heptylquinoline-4(1H)-ylidene)methyl)-PMI, and 9-((10-methylacridine-9(10H)-ylidene)methyl)-PMI, show a pronounced bathochromic shift of their electronic absorption with solvatochromism because of their intramolecular charge transfer. The solvatochromic behavior of these dyes is further confirmed by second-order nonlinear optical experiments. Remarkably high second-order nonlinear optical values (βHRS up to 1300 ± 50 × 10–30 esu at 880 nm in dichloromethane) are obtained by femtosecond hyper-Rayleigh scattering. The one-step synthesis together with the spectroscopic, solvatochromic, and nonlinear optical characteristics qualify these new types of perylene dyes as promising candidates for solvent polarity probes, photovoltaics, or nonlinear optical applications.

A new fluorescent probe for distinguishing Zn2+ and Cd2+ with high sensitivity and selectivity

“…Thus, the ICT effect is expected in this probe. 52,53 After combining with metal ions, the energy level of the ICT state is supposed to be reduced, leading to both spectra shift and fluorescence intensity variation. 54 The crucial point is that the reducing degree of the ICT state is related to the electron withdrawing ability of metal ions, thereby even minor electronic differences between cations may cause quite a significant spectra shift.…”

Study on the photophysical and electrochemical property and molecular simulation of broadly absorbing and emitting perylene diimide derivatives with large D–π–A structure

“…C1 and C2 were synthesized according to the literature. 19 Br-PDI (0.50 g, 0.65 mmol) and the quaternary intermediate QL (0.41 g, 1.30 mmol) were dissolved in 15 mL NMP in a Schlenk ask and were ushed with argon. The reaction mixture was heated to 115 C and a mixture of N-ethyldiisopropylamine (0.50 g, 3.90 mmol) and pyridine (0.62 g, 7.80 mmol) was added rapidly.…”

Structure–property relationship of donor–acceptor acridones – an optical, electrochemical and computational study

“…12 Acridone is a commercially available and modifiable building block but few reports have expanded this system to exploit its optical and electronic properties toward organic materials applications. [13][14][15][16] This literature gap is surprising because its p-extended congener, quinacridone, has been studied extensively and has proven to be a robust pigment molecule with low HOMO-LUMO energy gaps. 17,18 Previously, we reported an electron donating organic system using a phenothiazine core 19 however, their optical HOMO-LUMO energy gap was quite large (3.2 eV), limiting their use as visible-light chromophores.…”