Influence of benzothiophene acceptor moieties on the non-linear optical properties of pyreno-based chromophores: first-principles DFT framework.

Herein, a series of heterocyclic organic compounds (PYFD1-PYFD7) are designed with different acceptor moieties at the terminal position of a reference compound (PYFR) for nonlinear optical (NLO) active materials. The optoelectronic characteristics of the designed chromophores were investigated using density functional theory (DFT) calculations with the M06/6-311G(d,p) functional. Frontier molecular orbital (FMO) analysis revealed a significant decrease in the energy of the band gaps (2.340-2.602 eV) for the derivatives as compared to the PYFR reference compound (3.12 eV). An efficient transfer of charge from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO) was seen, which was further corroborated by the density of states (DOS) and transition density matrix (TDM) heat maps. The results of the global reactivity parameters (GRPs) indicated that all derivatives exhibited greater softness (σ = 0.384-0.427 eV) and lower hardness (η = 0.394-1.302 eV) as compared to PYFR, indicating a higher level of polarizability in the derivatives. Moreover, all of the derivatives showed significant findings in terms of nonlinear optical (NLO) results as compared to the reference chromophore. PYFD2 showed the most effective NLO response (α = 1.861 × 10-22 and ßtot = 2.376 × 10-28 esu), including a lowered band gap of 2.340 eV, the maximum softness value of 0.4273 eV, and the lowest hardness value of 1.170 eV as compared to other chromophores. The incorporation of different acceptors and thiophene as a π-spacer in this structural alteration significantly contributed to achieving remarkable NLO responses. Therefore, our findings may motivate experimentalists to synthesize these designed NLO active materials for the current advanced technological applications.

Use of benzothiophene ring to improve the photovoltaic efficacy of cyanopyridinone-based organic chromophores: a DFT study.

The benzothiophene based chromophores (A1D1-A1D5) with A-π-A configuration were designed via end-capped tailoring with benzothiophene type acceptors using reference compound (A1R). Quantum chemical calculations were accomplished at M06/6-311G(d,p) level to probe optoelectronic and photophysical properties of designed chromophores. Therefore, frontier molecular orbitals (FMOs), binding energy (Eb), open circuit voltage (Voc), transition density matrix (TDM), density of state (DOS) and UV-Vis analyses of A1R and A1D1-A1D5 were accomplished. The designed compounds (A1D1-A1D5) exhibited absorption values in the visible region as 616.316-649.676 nm and 639.753-665.508 nm in gas and chloroform phase, respectively, comparing with reference chromophore. An efficient charge transference from HOMO towards LUMO was found in A1D1-A1D5 chromophores which was further supported by TDM and DOS analyses. Among all chromophores, A1D2 exhibited unique characteristics such as reduced band gap (2.354 eV), higher softness (σ = 0.424 eV), lower exciton binding energy (0.491 eV) and maximum value of open circuit voltage (Voc = 1.981 V). Consequently, A1D2 may be considered as potential candidate for the development of optoelectronic devices. These analyses revealed that the studied compounds exhibited promising findings. They may be utilized in the realm of organic solar cells.

Heterocyclic Donor Moiety Effect on Optical Nonlinearity Behavior of Chrysene-Based Chromophores with Push-Pull Configuration via the Quantum Chemical Approach.

Organic-based nonlinear optical (NLO) materials may be used in many optical-electronic systems and other next-generation defense technologies. With the importance of NLO materials, a series of push-pull architecture (D-π-A) derivatives (DTMD2-DTMD6) were devised from DTMR1 through structural alteration of different efficient donor heterocyclic groups. Density functional theory-based computations were executed at the MPW1PW91/6-31G(d,p) level to explore the NLO behavior of the derivatives. To investigate the optoelectronic behavior of the said compounds, various analyses like the frontier molecular orbital (FMO), global reactivity parameters, density of state (DOS), absorption spectra (UV-vis), natural bond orbital, and transition density matrix (TDM) were performed. The derivatives have a smaller band gap (2.156-1.492 eV) and a larger bathochromic shift (λmax = 692.838-969.605 nm) as compared to the reference chromophore (ΔE = 2.306 eV and λmax = 677.949 nm). FMO analysis revealed substantial charge conduction out of the donor toward the acceptor via a spacer that was also shown by TDM and DOS analyses. All derivatives showed promising NLO results, with the maximum amplitude of linear polarizability ⟨α⟩ and first (ßtotal) and second (γtotal) hyperpolarizabilities over their reference chromophore. DTMD2 contained the highest ßtotal (7.220 × 10-27 esu) and γtotal (1.720 × 10-31 esu) values corresponding with the reduced band gap (1.492 eV), representing potential futures for a large NLO amplitude. This structural modification through the use of various donors has played a significant part in achieving promising NLO behavior in the modified compounds.

Synthesis, characterization and NLO properties of 1,4-phenylenediamine-based Schiff bases: a combined theoretical and experimental approach.

In the current study, three novel 1,4-phenylenediamine-based chromophores (3a-3c) were synthesized and characterized and then their nonlinear optical (NLO) characteristics were explored theoretically. The characterization was done by spectroscopic analysis, i.e. FT-IR, UV-Visible, and NMR spectroscopy, and elemental analysis. Notably, these chromophores exhibited UV-Visible absorption within the range of 378.635-384.757 nm in acetonitrile solvent. Additionally, the FMO findings for 3a-3c revealed the narrowest band gap (4.129 eV) for 3c. The GRPs for these chromophores were derived from HOMO-LUMO energy values, which showed correspondence with FMO results by depicting a minimum hardness (2.065 eV) for 3c. Among these compounds, 3c displayed the highest nonlinear behavior with maximum µtot, ßtot and γtot values of 4.79 D, 8.00 × 10-30 and 8.13 × 10-34 a.u., respectively. Our findings disclosed that the synthesized 1,4-phenylenediamine chromophores may be considered promising candidates for nonlinear optical materials, showing potential applications in the realm of optoelectronic devices.

Promising impact of push-pull configuration into designed octacyclic naphthalene-based organic scaffolds for nonlinear optical amplitudes: a quantum chemical approach.

In opto-electronics, non-fullerene (NF) derivatives are regarded as efficient non-linear optical (NLO) materials. The present investigation was based on designing NF naphthalene-based derivatives (PCMD1-D9) with D-π-A configuration from PCMR. DFT analysis at M06/6-311G (d,p) level was accomplished to explore the photonic behavior of PCMD1-D9 compounds. Various kind of analysis like; UV-Vis, density of state (DOS), natural bond orbitals (NBOs), transition density matrix (TDM) and frontier molecular orbitals (FMOs) analyses were accomplished to understand the NLO properties of said chromophores. The configuration change led to considerable charge distribution over highest occupied and lowest unoccupied molecular orbitals with minimum band difference. The energy gap trend for all the entitled compounds was observed as; PCMD8 < PCMD5 = PCMD9 < PCMD6 < PCMD7 < PCMD4 < PCMD3 < PCMD2 < PCMD1 with the least band gap of 2.048 eV in PCMD8 among all the compounds. The UV-Visible spectrum of the entitled chromophores manifested high values of λmax in derivatives contrary to PCMR. Additionally, NBO findings explored effective intramolecular charge transfer and maximum energy of stabilization (34.31 kcal/mol) for PCMD8 chromophore. The highest linear polarizability (<α>) and dipole moment (µtot) values were exhibited by PCMD5 at 2.712 × 10-22. and 1.995 × 10-17 esu, respectively. PCMD8 push-pull configured molecular entity exhibited highest first hyper-polarizability (ßtot) at 4.747 × 10-27 esu and second hyper-polarizability at 6.867 × 10-32 esu. Overall, all the formulated chromophores exhibited significant NLO results contrary to PCMR. Hence, through this structural tailoring via various acceptors, effective NLO materials were obtained for optoelectronic applications.

Multicomponent synthesis of pyrido[2,3-b]pyrazine derivatives: electrochemical DNA sensing, nonlinear optical properties and biological activity.

We synthesized novel pyrido[2,3-b]pyrazin based heterocyclic compounds (4-7) and their chemical structures were ascertained by spectral techniques (NMR, FT-IR). Besides experimental investigation, density functional theory (DFT) computations with B3LYP/6-31G(d,p) level of theory were executed to obtain spectroscopic and electronic properties. Nonlinear optical (NLO) properties, frontier molecular orbitals (FMOs), UV-visible, vibrational analysis, natural bond orbitals (NBOs), transition density matrix (TDM) and density of states (DOS) analyses of molecules (4-7) were accomplished at B3LYP/6-31G (d,p) level. Global reactivity parameters (GRPs) were correlated with the band gap (Egap) values; compound 7 with lower Egap (3.444 eV), exhibited smaller value of hardness (1.722 eV) with greater softness value (0.290 eV-1). The dipole moment (µ), average polarizability 〈α〉, first (ßtot) and second 〈γ〉 hyper-polarizabilities were calculated for compounds (4-7). Compound 7 showed less Egap, highest absorption wavelength and remarkable NLO response. The highest 〈α〉, ßtot and 〈γ〉 values for compound 7 were observed as 3.90 × 10-23, 15.6 × 10-30 and 6.63 × 10-35 esu, respectively. High NLO response revealed that pyrido[2,3-b]pyrazin based heterocyclic compounds had very remarkable contributions towards NLO technological applications. Further compounds (4-7) are utilized for the first time in electrochemical sensing of DNA, in vitro antioxidant and antiurease activity.

Theoretical Perspective toward Designing of 5-Methylbenzo [1,2-b:3,4-b':6,5-b″] trithiophene-Based Nonlinear Optical Compounds with Extended Acceptors.

A series of benzotrithiophene-based compounds (DCTM1-DCTM6) having D1-π1-D2-π2-A configuration were designed using a reference molecule (DCTMR) via incorporating pyrrole rings (n = 1-5) as the π-spacer (π2). Quantum chemical calculations were performed to determine the impact of the pyrrole ring on the nonlinear optical (NLO) behavior of the above-mentioned chromophores. The optoelectronic properties of the compounds were determined at the MW1PW91/6-311G(d,p) functional. Among all of the derivatives, DCTM5 exhibited the least highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) band gap (Eg) 0.968 eV with a high softness of 0.562 eV-1, and hence possessed the highest polarizability. Interestingly, transition density matrix (TDM) findings demonstrated that DCTM5 with an effective diagonal charge transmission proportion at the acceptor group supports the frontier molecular orbital (FMO) results. Additionally, the exciton binding energy values for DCTM1-DCTM6 were found to be less than that for DCTMR and thus, the effective charge transfer was examined in the derivatives. All of the derivatives exhibited effective NLO outcomes with the highest magnitude of linear polarizability ⟨α⟩, and first (ßtot) and second (γtot) hyperpolarizabilities relative to the parent compound. Nevertheless, the highest ßtot and γtot were obtained for DTCM1 and DTCM6, 7.0440 × 10-27 and 22.260 × 10-34 esu, respectively. Hence, through this structural tailoring with a pyrrole spacer, effective NLO materials can be obtained for optoelectronic applications.

Influence of azacycle donor moieties on the photovoltaic properties of benzo[c][1,2,5]thiadiazole based organic systems: a DFT study.

Fullerene free organic chromophores are widely utilized to improve the efficacy of photovoltaic materials. Herein, we designed D-π-A-π-D form chromophores (TAZD1-TAZD5) via end-capped redistribution of donor moieties by keeping the same π-bridge and central acceptor unit for organic solar cells (OSCs). To analyze the photovoltaic characteristics of these derivatives, DFT estimations were accomplished at B3LYP/6-311 G (d,p) functional. Different investigations like frontier molecular orbital (FMO), absorption spectra (UV-Vis), density of states (DOS), binding energy (Eb), open circuit voltage (Voc), and transition density matrix (TDMs) were performed to examine the optical, photophysical and electronic characteristics of afore-mentioned chromophores. A suitable band gap (∆E = 2.723-2.659 eV) with larger bathochromic shift (λmax = 554.218-543.261 nm in acetonitrile) was seen in TAZD1-TAZD5. An effective charge transference from donor to acceptor via spacer was observed by FMO analysis which further supported by DOS and TDM. Further, lower binding energy values also supported the higher exciton dissociation and greater CT in TAZD1-TAZD5. Among all the designed chromophores, TAZD5 exhibited the narrowest Egap (2.659 eV) and maximum red-shifted absorption in solvent as well as gas phase i.e. 554.218 nm and 533.219 nm, respectively which perhaps as a result of the phenothiazine-based donor group (MPT). In a nutshell, all the tailored chromophores can be considered as efficient compounds for promising OSCs with a good Voc response, interestingly, TAZD5 is found to be excellent chromophores as compared to all these designed compounds.

Quantum Chemical Exploration of A-π1-D1-π2-D2-Type Compounds for the Exploration of Chemical Reactivity, Optoelectronic, and Third-order Nonlinear Optical Properties.

Organic compounds exhibit significant nonlinear optical (NLO) properties and can be utilized in various areas like optical parameters, fiber optics, and optical communication. Herein, a series of chromophores (DBTD1-DBTD6) with an A-π1-D1-π2-D2 framework was derived from a prepared compound (DBTR) by varying the structure of π-spacer and terminal acceptor. The DBTR and its investigated compounds were optimized at the M06/6-311G(d,p) level of theory. Frontier molecular orbitals (FMOs), nonlinear optical (NLO) properties, global reactivity parameters (GRPs), natural bonding orbital (NBO), transition density matrix (TDM), molecular electrostatic potential (MEP), and natural population analysis (NPA) were accomplished at the abovementioned level to describe the NLO findings. DBTD6 has the lowermost band gap (2.131 eV) among all of the derived compounds. The decreasing order of highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) energy gap values was DBTR > DBTD1 > DBTD2 > DBTD3 > DBTD4 > DBTD5 > DBTD6. The NBO analysis was carried out to describe noncovalent interactions such as conjugative interactions and electron delocalization. From all of the examined substances, DBTD5 showed the highest λmax value at 593.425 nm (in the gaseous phase) and 630.578 nm (in chloroform solvent). Moreover, the ßtot and ⟨γ⟩ amplitudes of DBTD5 were noticed to be relatively greater at 1.140 × 10-27 and 1.331 × 10-32 esu, respectively. So, these outcomes disclosed that DBTD5 depicted the highest linear and nonlinear properties in comparison to the other designed compounds, which underlines that it could make a significant contribution to hi-tech NLO devices.

Design, Synthesis, and Density Functional Theory Studies of Indole Hydrazones as Colorimetric "Naked Eye" Sensors for F Ions.

A new series of sensors SM-1 to SM-3 was designed and synthesized using indole carboxaldehydes (2a-2c) and 2,4-dinitrophenyl hydrazine. Accompanied by the synthesis, density functional theory investigation was also accomplished at the M06-2X/6-311G+(d,p) functional. A reduction in band gap (ΔE = 4.702-4.230 eV) along with a bathochromic shift (λmax = 433.223-471.584 nm) was seen in deprotonated chromophores than their neutral sensors. Further, significant charge transference from indole toward dinitrophenyl hydrazine was also examined. Global reactivity parameters also expressed the greater stability of sensors than that of their deprotonated form. SM-3 displayed high selectivity toward F ions as compared to SM-1 and SM-2, which respond to both F- and CN- ions. The electronic absorption spectrum was recorded in CH3CN. The sensor SM-3 showed high selectivity toward F- ions with a low detection limit (8.69 × 10-8), and the binding constant for SM-3 was determined as 7.7 × 105. The sensor displayed naked eye views as the color of solution changed from mustard to purple with a red shift of 96 nm. The mechanism suggests deprotonation from the NH group, which was confirmed by 1H NMR. The sensor is found to be useful for detection of F- ions in the real sample and for analytical application (test strip).

Efficient Synthesis, Spectroscopic Characterization, and Nonlinear Optical Properties of Novel Salicylaldehyde-Based Thiosemicarbazones: Experimental and Theoretical Studies.

Currently, we reported the synthesis of six novel salicylaldehyde-based thiosemicarbazones (BHCT1-HBCT6) via condensation of salicylaldehyde with respective thiosemicarbazide. Through various spectroscopic methods, UV-visible and NMR, the chemical structures of BHCT1-HBCT6 compounds were determined. Along with synthesis, a computational study was also performed at the M06/6-31G(d,p) functional. Various analyses such as natural bond orbital (NBO) analysis, natural population analysis, frontier molecular orbital (FMO) analysis, and molecular electrostatic potential surfaces were carried out to understand the nonlinear optical (NLO) characteristics of the synthesized compounds. Additionally, a comparative study was carried out between DFT and experimental results (UV-vis study), and a good agreement was observed in the results. The energy gap calculated through FMOs was found to be in decreasing order as 4.505 (FHCT2) > 4.499 (HBCT6) > 4.497 (BHCT1) = 4.497(HMCT5) > 4.386 (CHCT3) > 4.241(AHCT4) in eV. The global reactivity parameters (GRPs) were attained through E HOMO and E LUMO, which described the stability and hardness of novel compounds. The NBO approach confirmed the charge delocalization and stability of the molecules. Among all the investigated compounds, a larger value (557.085 a.u.) of first hyperpolarizability (ßtot) was possessed by CHCT3. The NLO response (ßtot) of BHCT1-HBCT6 was found to be 9.145, 9.33, 13.33, 5.43, 5.68, and 10.13 a.u. times larger than that of the standard para-nitroaniline molecule. These findings ascertained the potential of entitled ligands as best NLO materials for a variety of applications in modern technology.

Efficient Synthesis of Imine-Carboxylic Acid Functionalized Compounds: Single Crystal, Hirshfeld Surface and Quantum Chemical Exploration.

Two aminobenzoic acid based crystalline imines (HMBA and DHBA) were synthesized through a condensation reaction of 4-aminobenzoic acid and substituted benzaldehydes. Single-crystal X-ray diffraction was employed for the determination of structures of prepared Schiff bases. The stability of super molecular structures of both molecules was achieved by intramolecular H-bonding accompanied by strong, as well as comparatively weak, intermolecular attractive forces. The comparative analysis of the non-covalent forces in HMBA and DHBA was performed by Hirshfeld surface analysis and an interaction energy study between the molecular pairs. Along with the synthesis, quantum chemical calculations were also accomplished at M06/6-311G (d, p) functional of density functional theory (DFT). The frontier molecular orbitals (FMOs), molecular electrostatic potential (MEP), natural bond orbitals (NBOs), global reactivity parameters (GRPs) and natural population (NPA) analyses were also carried out. The findings of FMOs found that Egap for HMBA was examined to be smaller (3.477 eV) than that of DHBA (3.7933 eV), which indicated a greater charge transference rate in HMBA. Further, the NBO analysis showed the efficient intramolecular charge transfer (ICT), as studied by Hirshfeld surface analysis.

Enhancing the Photovoltaic Properties via Incorporation of Selenophene Units in Organic Chromophores with A2-π2-A1-π1-A2 Configuration: A DFT-Based Exploration.

Currently, polymer organic solar cells (POSCs) are widely utilized due to their significant application, such as low-cost power conversion efficiencies (PCEs). Therefore, we designed a series of photovoltaic materials (D1, D2, D3, D5 and D7) by the incorporation of selenophene units (n = 1-7) as π1-spacers by considering the importance of POSCs. Density functional theory (DFT) calculations were accomplished at MPW1PW91/6-311G (d, p) functional to explore the impact of additional selenophene units on the photovoltaic behavior of the above-mentioned compounds. A comparative analysis was conducted for designed compounds and reference compounds (D1). Reduction in energy gaps (∆E = 2.399 - 2.064 eV) with broader absorption wavelength (λmax = 655.480 - 728.376 nm) in chloroform along with larger charge transference rate was studied with the addition of selenophene units as compared to D1. A significantly higher exciton dissociation rate was studied as lower values of binding energy (Eb = 0.508 - 0.362 eV) were noted in derivatives than in the reference (Eb = 0.526 eV). Moreover, transition density matrix (TDM) and density of state (DOS) data also supported the efficient charge transition origination from HOMOs to LUMOs. Open circuit voltage (Voc) was also calculated for all the aforesaid compounds to check the efficiency, and significant results were seen (1.633-1.549 V). All the analyses supported our compounds as efficient POSCs materials with significant efficacy. These compounds might encourage the experimental researchers to synthesize them due to proficient photovoltaic materials.

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.

Effect of different end-capped donor moieties on non-fullerenes based non-covalently fused-ring derivatives for achieving high-performance NLO properties.

A series of derivatives (DOCD2-DOCD6) with D-π-A configuration was designed by substituting various efficient donor moieties via the structural tailoring of o-DOC6-2F. Quantum-chemical approaches were used to analyze the optoelectronic properties of the designed chromophores. Particularly, M06/6-311G(d,p) functional was employed to investigate the non-linear optical (NLO) response (linear polarizability ⟨α⟩, first (ßtot) and second ([Formula: see text]tot) order hyperpolarizabilities) of the designed derivatives. A variety of analyses such as frontier molecular orbital (FMO), absorption spectra, transition density matrix (TDMs), density of states (DOS), natural bond orbital (NBO) and global reactivity parameters (GRPs) were employed to explore the optoelectronic response of aforementioned chromophores. FMO investigation revealed that DOCD2 showed the least energy gap (1.657 eV) among all the compounds with an excellent transference of charge towards the acceptor from the donor. Further, DOS pictographs and TDMs heat maps also supported FMO results, corroborating the presence of charge separation states along with efficient charge transitions. NBO analysis showed that π-linker and donors possessed positive charges while acceptors retained negative charges confirming the D-π-A architecture of the studied compounds. The λmax values of designed chromophores (659.070-717.875 nm) were found to have broader spectra. The GRPs were also examined utilizing energy band gaps of EHOMO and ELUMO for the entitled compounds. Among all the derivatives, DOCD2 showed the highest values of ßtot (7.184 × 10-27 esu) and [Formula: see text]tot (1.676 × 10-31 esu), in coherence with the reduced band gap (1.657 eV), indicating future potentiality for NLO materials.

First theoretical framework for highly efficient photovoltaic parameters by structural modification with benzothiophene-incorporated acceptors in dithiophene based chromophores.

Now a days, researchers are constantly doing efforts to upgrade the performance of solar based devices with the aim of increasing the role of photovoltaic materials in modern hi-tech optoelectronic applications. Realizing the recent energy conditions across the globe, research is diverted from fullerene to non-fullerene electron acceptor moieties in this era, considering their remarkable contribution in organic solar cells (OSCs). Therefore, we designed seven novel non-fullerene fused ring electron acceptor chromophores (MD2-MD8) from DOC2C6-2F by structural tailoring with different acceptors at end-capped units. DFT study was performed at B3LYP functional to discover the opto-electronic characteristics of the newly tailored chromophores. Various analysis such as frontier molecular orbitals (FMOs), transition density matrix (TDM), density of states (DOS), binding energy (Eb), reorganization energy, open circuit voltage (Voc) was carried out to comprehend the photovoltaic response of MD2-MD8. Decrease in band gaps (1.940-1.571 eV) with wider absorption spectrum (725.690-939.844 nm in chloroform) along with greater charge transfer rate from HOMO towards LUMO were examined in derivatives as compared to MR1 (Egap = 1.976 eV, λmax = 738.221 nm) except MD7. Further, in all derivatives, smaller values of Eb (0.252-0.279 eV) were examined than that of reference (0.296 eV). These lower binding energy values of MD2-MD8 indicated the higher rate of excitation dissociation with lager charger transfer rate than MR1, which further supported by DOS and TDM analyses. Additionally, least reorganization energy in the aforesaid compounds for hole with electron was also inspected. Moreover, Voc a good photovoltaic response was noted for all studied compounds which indicated that these compounds are suitable to synthesize OSCs in future.

Enriching NLO efficacy via designing non-fullerene molecules with the modification of acceptor moieties into ICIF2F: an emerging theoretical approach.

Non-fullerene (NF)-based compounds have attracted much attention as compared to fullerene-based materials because of their promising optoelectronic properties, lower synthetic cost and greater stability. Usually, the end-capped groups have a promising impact in magnifying the nonlinear optical (NLO) characteristics in the non-fullerene molecules. Based on this, a series of new NLO active non-fullerene molecules (NFAD2-NFAD6) have been established. The non-fullerene molecules (NFAD2-NFAD6) were designed by end-capped modification in acceptor moieties of the reference (NFAR1), while donor and π-bridge moieties were kept the same in the entire series. Quantum chemistry-based calculations at the M06/6-311G(d,p) level were done to determine the NLO characteristics and for other supportive analyses. The acceptor and donor moieties were utilized at the opposite terminals of NFAD2-NFAD6, which proved to be an effective approach in tuning the FMO band gap. Overall the results of natural bond orbital (NBO), density of state (DOS) and transition density matrices (TDMs) analyses supported the NLO properties of the designed compounds. Among all the studied compounds, NFAD4 was proven to be the most suitable candidate due to its promising NLO properties, well supported by a lower bandgap of 1.519 eV and a maximum absorption wavelength of 999.550 nm. Therefore, NFAD4 was reported with greater amplitude of dipole polarizability (10.429 e.s.u), average polarizability (2.953 × 10-22 e.s.u), first hyperpolarizability (13.16 × 10-27 e.s.u.) and second hyperpolarizability (2.150 × 10-31 e.s.u.) than other derivatives and NFAR1. Subsequently, the present study depicted the significance of utilizing different non-fullerene (NF)-based acceptor moieties to achieve the promising NLO material. This computational study may lead towards new plausible pathways for researchers to design potent NLO substances for impending hi-tech applications.

Exploration of the Intriguing Photovoltaic Behavior for Fused Indacenodithiophene-Based A-D-A Conjugated Systems: A DFT Model Study.

Many researchers are engaged nowadays in developing efficient photovoltaic materials to accomplish the demand of modern technology. Nonfullerene small molecular acceptors (NF-SMAs) show potential photovoltaic performance, accelerating the development of organic solar cells (OSCs). Herein, the first theoretical designing of a series of indacenodithiophene-based (IDIC1-IDIC6) acceptor chromophores was done by structural tailoring with various well-known acceptors from the recently synthesized IDICR molecule. For the selection of the best level of density functional theory (DFT), various functionals such as B3LYP, M06-2X, CAM-B3LYP, and ωB97XD with the 6-311G(d,p) basis set were used for the UV-visible analysis of IDICR. Consequently, UV-visible results revealed that an interesting agreement was found between experimental and DFT-based values at the B3LYP level. Therefore, quantum chemical investigations were executed at the B3LYP/6-311G(d,p) level to evaluate the photovoltaic and optoelectronic properties. Structural tailoring with various acceptors resulted in a narrowing of the energy gap (2.245-2.070 eV) with broader absorption spectra (750.919-660.544 nm). An effective transfer of charge toward lowest unoccupied molecular orbitals (LUMOs) from highest occupied molecular orbitals (HOMOs) was studied, which played a crucial role in conducting materials. Further, open circuit voltage (V oc) analysis was performed with respect to HOMO PBDB-T -LUMOACCEPTOR, and all of the derivatives exhibited a comparable value of voltage with that of the parent chromophore. Lower reorganization energies in titled chromophores for holes and electrons were examined, which indicated the higher rate of mobility of charges. Interestingly, all of the designed chromophores exhibited a preferable optoelectronic response compared to the reference molecule. Therefore, this computed framework demonstrates that conceptualized chromophores are preferable and might be used to build high-performance organic solar cells in the future.

Structural modulation of π-conjugated linkers in D-π-A dyes based on triphenylamine dicyanovinylene framework to explore the NLO properties.

A donor-π-acceptor type series of Triphenylamine-dicyanovinylene-based chromophores (DPMN1-DPMN11) was designed theoretically by the structural tailoring of π-linkers of experimentally synthesized molecules DTTh and DTTz to exploit changes in the optical properties and their nonlinear optical materials (NLO) behaviour. Density functional theory (DFT) computations were employed to understand the electronic structures, absorption spectra, charge transfer phenomena and the influence of these structural modifications on NLO properties. Interestingly, all investigated chromophores exhibited lower band gap (2.22-2.60 eV) with broad absorption spectra in the visible region, reflecting the remarkable NLO response. Furthermore, natural bond orbital (NBO) findings revealed a strong push-pull mechanism in DPMN1-DPMN11 as donor and π-conjugates exhibited positive, while all acceptors showed negative values. Examination of electronic transitions from donor to acceptor moieties via π-conjugated linkers revealed greater linear (〈α〉 = 526.536-641.756 a.u.) and nonlinear (ß tot = 51 313.8-314 412.661 a.u.) response. It was noted that the chromophores containing imidazole in the second p-linker expressed greater hyperpolarizability when compared with the ones containing pyrrole. This study reveals that by controlling the type of π-spacers, interesting metal-free NLO materials can be designed, which can be valuable for the hi-tech NLO applications.