Role of donors in triggering second order non-linear optical properties of non-fullerene FCO-2FR1 based derivatives: A theoretical perspective.

The organic compounds are known as an emerging class in the field of nonlinear optical (NLO) materials. In this paper, D-π-A configured oxygen containing organic chromophores (FD2-FD6) were designed by incorporating various donors in the chemical structure of FCO-2FR1. This work is also inspired by the feasibility of FCO-2FR1 as an efficient solar cell. Theoretical approach involving DFT functional i.e., B3LYP/6-311G(d,p) was utilized to achieve useful information regarding their electronic, structural, chemical and photonic properties. The structural modifications revealed significant electronic contribution in designing HOMOs and LUMOs for the derivatives with lowered energy gaps. The lowest HOMO-LUMO band gap obtained was 1.223 eV for FD2 compound in comparison to the reference molecule (FCO-2FR1) i.e., 2.053 eV. Moreover, the DFT findings revealed that the end-capped substituents play a key role in enhancing the NLO response of these push-pull chromophores. The UV-Vis spectra of tailored molecules revealed larger λ max values than the reference compound. Furthermore, strong intramolecular interactions showed the highest stabilization energy (28.40 kcal mol-1) for FD2 in the natural bond orbitals (NBOs) transitions, combined with the least binding energy (-0.432 eV). Successfully, the NLO results were favorable for the same chromophore (FD2) which showed the highest value for dipole moment (µ tot = 20.049 D) and first hyper-polarizability (ß tot = 11.22 × 10-27 esu). Similarly, the largest value for linear polarizability ⟨α⟩ was obtained as 2.936 × 10-22 esu for FD3 compound. Overall, the designed compounds were calculated with greater NLO values as compared to FCO-2FR1. The current study may provoke the researchers towards designing of highly efficient NLO materials via using the suitable organic linking species.

First theoretical probe for efficient enhancement of optical nonlinearity via structural modifications into phenylene based D-π-A configured molecules.

The design of nonlinear optical (NLO) materials using conjugated molecules via different techniques is reported in the literature to boost the use of these systems in NLO. Therefore, in the current study, designed phenylene based non-fullerene organic compounds with a D-π-A framework were selected for NLO investigation. The initial compound (PMD-1) was taken as a reference and its seven derivatives (PMDC2-PMDC8) were made by introducing different acceptor moieties into the chemical structure of PMD-1. To explain the NLO findings, frontier molecular orbital (FMO), transition density matrix (TDM), density of states (DOS), natural bond orbital (NBO) and UV-Vis study of the title compounds was executed by applying the PBE1PBE functional with the 6-311G(d,p) basis set. The descending order of band gaps (E gap) was reported as PMDC7 (2.656) > PMDC8 (2.485) > PMD-1 (2.131) > PMDC3 (2.103) > PMDC2 (2.079) > PMDC4 (2.065) > PMDC5 (2.059) > PMDC6 (2.004), in eV. Global reactivity parameters (GRPs) were associated with E gap values as PMDC6 with the lowest band gap showed less hardness (0.0368 E h) and high softness (13.5785 E h). The UV-Vis investigation revealed that the maximum λ max (739.542 nm) was exhibited by PMDC6 in dichloromethane (DCM) as compared to other derivatives. Additionally, natural bond orbital (NBO) based findings revealed that PMDC6 exhibited the highest stability value (34.98 kcal mol-1) because of prolonged hyper-conjugation. The dipole moment (µ), average linear polarizability 〈α〉, first hyperpolarizability (ß tot) and second hyperpolarizability (γ tot) were evaluated for the reference and its derivatives. Consequently, among the designed compounds, the highest ß tot (4.469 × 10-27 esu) and γ tot (5.600 × 10-32 esu) values were shown by PMDC6. Hence, it's concluded from said results that these structural modifications proved PMDC6 as the best second and third order NLO candidate for various applications like fiber optics, signal processing and data storage.

Synthesis, nonlinear optical analysis and DFT studies of D-π-D and A-π-A configured Schiff bases derived from bis-phenylenediamine.

Herein, an integral approach has been made towards the exploration of electronic and structural parameters of four synthesized (DMA with an A-π-A configuration and DMM, DAM, and DMD with a D-π-D configuration) and one designed (DMB-D) novel Schiff base compounds. Bis phenylenediamine derivatives were prepared by condensation of 4,5-dimethyl-o-phenylenediamine (1) with various substituted benzaldehydes (2a-d). The structures of compounds were confirmed by spectroscopic techniques, i.e., UV-visible, FT-IR, and NMR spectroscopy. The DFT-based analysis of entitled compounds was performed via density functional theory utilizing the M06-2X functional in conjugation with the 6-311G(d,p) basis set to acquire geometrical parameters, natural bonding orbital (NBO), the density of states (DOS), non-linear optical (NLO), molecular electrostatic potential (MESP), and natural population analyses. The smallest band gap of (5.446 eV) was noted for DMAvia frontier molecular orbital (FMO) analysis. GRPs were obtained with the aid of E gap values as DMA with the lowest band gap displayed a small magnitude of hardness (2.723 eV) and a large magnitude of softness (0.183 eV). The ß tot values of DMA, DMM, DMB-D, DAM, and DMD were 56.95, 0.43, 2.53, 8.98, and 68.47 times larger than urea (ß tot = 3.71 × 10-31 e.s.u.), respectively. The observed fascinating NLO properties of these novel compounds might be helpful for further advancement in non-linear optics.

Synthesis, spectroscopic, SC-XRD/DFT and non-linear optical (NLO) properties of chromene derivatives.

In the present study, we reported the efficient synthesis of novel, heterocyclic, coumarin-based pyrano-chromene derivatives, 2-amino-8-methyl-5-oxo-4-[2-(2-oxo-2H-chromen-3-ylmethoxy)-phenyl]-4H,5H-pyrano[3,2-c]chromene-3-carbonitrile (4a) and 2-amino-8-methyl-5-oxo-4-[2-(2-oxo-2H-chromen-3-ylmethoxy)-phenyl]-4H,5H-pyrano[3,2-c]chromene-3-carboxylic acid methyl ester (4b). The chemical structures of synthesized compounds were resolved by employing various spectroscopic techniques like UV-Vis, FT-IR, 1H & 13C NMR, and single crystal X-ray diffraction (SC-XRD) analysis. The compounds; 4a and 4b, with appealing π-bonded skeleton were further analyzed in terms of their electronic and structural aspects using an integral approach of density functional theory (DFT) and time-dependent DFT (TD/DFT). The methodology: M06-2X/6-31G(d,p) level of theory was applied to compare their experimental data with theoretical outcomes using quantum chemical analysis. The frontier molecular orbitals (FMOs) study revealed that, 4a possesses a low band gap (5.168 eV) as compared to 4b (6.308 eV). Global reactivity parameters were associated with E gap values as 4a, with the lowest band gap showed the smaller value of hardness (0.094 eV) and a larger value of softness (5.266 eV). The non-linear optical (NLO) insight exhibited that, the average polarizability 〈α〉 and second hyperpolarizability (γ tot) were observed in 4a as 6.77005 × 10-23 and 0.145 × 104 esu, respectively. Overall, the computational studies suggest that the investigated compounds have distinct NLO properties.