Design of Near-Infrared Dyes Based on π-Conjugation System Extension. Theoretical Evaluation of Arylimidazole Derivatives of Perylene Chromophore

Abstract

To design the near-infrared (NIR) dyes, the electronic absorption spectra of arylimidazoleintroduced 3,4,9,10-perylenetetracarboxylic dianhydride and its imide derivatives (PTCAIs) have been theoretically elucidated by using the molecular orbital (MO) calculation. An arylimidazole introduction causes a longer shift of the absorption wavelength (bathochromic shift) by destabilization of the HOMO level. The HOMO level of aryl groups (e.g., benzene and naphthalene) is close to the energy of PTCAI's HOMO; therefore, new orbitals which are characterized as a mixture of each orbital's features are generated by this large orbital interaction. The absorption wavelength shift depends not only on a HOMO level of the aryl group (π-conjugation size), but also on its pattern. With the bathochromic shift of the absorption spectrum, the transition is characterized as more intense of the charge-transfer (CT) property rather than the π-π* excitation on the perylene moiety.

Hole‐Transfer Dyads and Triads Based on Perylene Monoimide, Quaterthiophene, and Extended Tetrathiafulvalene

“…The perylene imide dye displays an intense absorption band at around 530 nm, which corresponds to a p!p* transition, the vibronic bands of which are still visible in the spectrum of trimethylsilylacetylene-perylene imide 2. [51,52] Quaterthiophene exhibits a broad p!p* transition at www.chemeurj.org around 400 nm located in the same region as those of the extended TTF. The absorption bands of exTTF are also attributed to p!p* transitions characterized by significant charge transfer from the dithiolium units to the central aromatic core.…”

Positional Effect of Phenylene Moiety on a Certain Perylene Chromophore: A Semiempirical Treatment

“…It has been reported that the diimide (3) absorption wavelength and intensity is unaffected by the change of its imide substituents (16,17). However, fusion of the benzimidazole moiety generally causes a bathochromic shift and cis-and trans-bis-derivatives have the same λ max values (1,18). Theoretically, the fusion of such a moiety to produce the bis-, (2), or mono-derivative should result in a bathochromic shift due to extended conjugation as compared to (3).…”

“…Recently, near-infrared (NIR) materials having the perylene core have attracted the interest of many scientists (1)(2)(3)(4)(5)(6). In many applications and devices these materials have been the key component (3,4).…”

“…In the past some calculations were performed on these system, e.g., PPP-MO (10), INDO/S (1, 11), AM1 (1,11), etc.…”

Positional Effect of Nitrogen Substitution on a Certain Perylene Chromophore-a Semiempirical Treatment

“…Near-infrared (NIR) materials having the perylene core have been the focus of many scientists (1)(2)(3)(4)(5)(6). Those materials play a key role in various optoelectronic devices.…”