Rational Design and Investigation of Nonlinear Optical Response Properties of Pyrrolopyrrole Aza-BODIPY-Based Novel Push-Pull Chromophores

19 February 2024, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Intramolecular charge transfer (ICT)-based chromophores are highly sought for designing near-Infrared (NIR) absorbing and emitting dyes, as well as designing chromophores for nonlinear optical (NLO) applications. The properties of these so-called ‘push-pull’ molecules could be tuned easily through modification of the electronic donor (D) and acceptor (A) groups as well as by the π-conjugating linker. This study presents rational design and quantum chemical investigation of the correlation between the structural attributes, electro-optical properties, and NLO characteristics of molecules with a D–π–A framework for applications in photonics. The one- and two-photon absorption (2PA), average linear polarizability (αav) as well as the first hyperpolarizability (β) of novel chromophores consisting of a Dimeric aza-Boron Dipyrromethene (aza-BODIPY) analogue known as pyrrolopyrrole aza-BODIPY (PPAB) as acceptor and Triphenylamine (TPA) or Diphenylamine (DPA) as electronic donor with thienyl or phenylene groups as linkers are studied. Additionally, the Hyper-Rayleigh Scattering (βHRS) which enables to directly estimate the second-order NLO properties is also calculated for these compounds with 1064 nm excitation in Acetonitrile solvent. Significant increase in the β with increasing solvent polarity indicates the role of ICT in shaping NLO response of these molecules. The two-photon absorption cross-section of studied molecules could also be enhanced through modulation of donor and linker combinations. Our findings show that the D–π–A molecules designed in the present work exhibit significantly larger hyperpolarizabilities values, compared to the standard p-Nitroaniline, making them suitable candidates for future NLO applications.


Intramolecular Charge Transfer
Nonlinear Optical Response
Two-photon absorption

Supplementary materials

Supplementary material for Rational Design and Investigation of Nonlinear Optical Response Properties of Pyrrolopyrrole Aza-BODIPY-Based Novel Push-Pull Chromophores
The supplementary material contains absorption data comparison using different functionals with the experimental provided data for : D–π–A-π–D framework containing molecules along with values of μ, α_av, β_total and β_vec, obtained using the ω*B97XD tuned functional and 6-31g* basis set, HOMO-LUMO energies of the PPAB molecules in different solvents with varying polarity and the electron density images of the molecules.


Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.