Molecular Engineering Research Articles

Light-Induced Living Polymer Networks with Adaptive Functional Properties.

The advent of covalent adaptable networks (CANs) through the incorporation of dynamic covalent bonds has led to unprecedented properties of macromolecular systems, which can be engineered at the molecular level. Among the various types of stimuli that can be used to trigger chemical changes within polymer networks, light stands out for its remote and spatiotemporal control under ambient conditions. However, most examples of photoactive CANs need to be transparent and they exhibit slow response, side reactions, and limited light penetration. In this vein, it is interesting tounderstand how molecular engineering of optically active dynamic linkages that offer fast response to visible light can impart "living" characteristics to CANs, especially in opaque systems. Here, the use of carbazole-based thiuram disulfides (CTDs) that offer dual reactivity as photoactivated reshuffling linkages and iniferters under visible light irradiation is reported. The fast response to visible light activation of the CTDs leads to temporal control of shape manipulation, healing, and chain extension in the polymer networks, despite the lack of optical transparency. This strategy charts a promising avenue for manipulating multifunctional photoactivated CANs in a controlled manner.

Axial Phenoxylation of Aluminum Phthalocyanines for Improved Cannabinoid Sensitivity in OTFT Sensors.

Cannabis producers, consumers, and regulators need fast, accurate, point-of-use sensors to detect Δ9-tetrahydrocannabinol (THC) and cannabidiol (CBD) from both liquid and vapor source samples, and phthalocyanine-based organic thin-film transistors (OTFTs) provide a cost-effective solution. Chloro aluminum phthalocyanine (Cl-AlPc) has emerged as a promising material due to its unique coordinating interactions with cannabinoids, allowing for superior sensitivity. This work explores the molecular engineering of AlPc to tune and enhance these interactions, where a series of novel phenxoylated R-AlPcs are synthesized and integrated into OTFTs, which are then exposed to THC and CBD solution and vapor samples. While the R-AlPc substituted molecules have a comparable baseline device performance to Cl-AlPc, their new crystal structures and weakened intermolecular interactions increase sensitivity to THC. Grazing-incidence wide-angle X-ray scattering (GIWAXS) and atomic force microscopy (AFM) are used to investigate this film restructuring, where a significant shift in the crystal structure, grain size, and film roughness is detected for the R-AlPc molecules that do not occur with Cl-AlPc. This significant crystal reorganization and film restructuring are the driving force behind the improved sensitivity to cannabinoids relative to Cl-AlPc and demonstrate that analyte-semiconductor interactions can be enhanced through chemical modification to create more responsive OTFT sensors.

A Tandem-Locked Chemiluminescent Probe for Imaging of Tumor-Associated Macrophage Polarization.

Tumor-associated macrophages (TAMs) play a role in both pro- and anti-tumor functions; and the targeted polarization from M2 to M1 TAMs has become an effective therapy option. Although detection of M1 TAMs is imperative to assess cancer immunotherapeutic efficacy, existing optical probes suffer from shallow tissue penetration depth and poor specificity toward M1 TAMs. Herein, we report a tandem-locked NIR chemiluminescent (CL) probe for specific detection of M1 TAMs. Through a combined molecular engineering approach via both atomic alternation and introduction of electron-withdrawing groups, near-infrared (NIR) chemiluminophores are screened out to possess record-long emission (over 800 nm), record-high CL quantum yield (2.7 % einstein/mol), and prolonged half-life (7.7 h). Based on an ideal chemiluminophore, the tandem-locked probe (DPDGN) is developed to only activate CL signal in the presence of both tumour (γ-glutamyl transpeptidase) and M1 macrophage biomarkers (nitric oxide). Such a tandem-lock design ensures its high specificity towards M1 macrophages in the tumor microenvironment over those in normal tissues or peripheral blood. Thus, DPDGN permits noninvasive imaging and tracking of M1 TAM in the tumor of living mice during R837 treatment, showing a good correlation with ex vivo methods. This study not only reports a new molecular approach towards highly efficient chemiluminophores but also reveals the first tandem-locked CL probes for enhanced imaging specificity.

A Tandem‐Locked Chemiluminescent Probe for Imaging of Tumor‐Associated Macrophage Polarization

AbstractTumor‐associated macrophages (TAMs) play a role in both pro‐ and anti‐tumor functions; and the targeted polarization from M2 to M1 TAMs has become an effective therapy option. Although detection of M1 TAMs is imperative to assess cancer immunotherapeutic efficacy, existing optical probes suffer from shallow tissue penetration depth and poor specificity toward M1 TAMs. Herein, we report a tandem‐locked NIR chemiluminescent (CL) probe for specific detection of M1 TAMs. Through a combined molecular engineering approach via both atomic alternation and introduction of electron‐withdrawing groups, near‐infrared (NIR) chemiluminophores are screened out to possess record‐long emission (over 800 nm), record‐high CL quantum yield (2.7 % einstein/mol), and prolonged half‐life (7.7 h). Based on an ideal chemiluminophore, the tandem‐locked probe (DPDGN) is developed to only activate CL signal in the presence of both tumour (γ‐glutamyl transpeptidase) and M1 macrophage biomarkers (nitric oxide). Such a tandem‐lock design ensures its high specificity towards M1 macrophages in the tumor microenvironment over those in normal tissues or peripheral blood. Thus, DPDGN permits noninvasive imaging and tracking of M1 TAM in the tumor of living mice during R837 treatment, showing a good correlation with ex vivo methods. This study not only reports a new molecular approach towards highly efficient chemiluminophores but also reveals the first tandem‐locked CL probes for enhanced imaging specificity.

Exploaration of the influence of end-capped structural modification on photovoltaic properties of selenopheno-thiophene core based non-fullerene chromophores: A DFT study

In current study, six novel selenopheno-thiophene (ST) core-based chromophores (SePTD1- SePTD6) with A-D-A configuration were designed via structural tailoring with terminal acceptors of SePTR. The optoelectronic and photovoltaic properties of SePTD1-SePTD6 were explored through TDDFT/DFT approaches. The B3LYP/6–31 G(d,p) level was chose through benchmarked study with the help of DFT and experimental UV-Vis values of SePTR. All tailored chromophores exhibited a comparatively smaller band gap (2.144–2.003 eV), along with a significant bathochromic shift (676.8–724.2 nm) and an increased rate of charge transference then reference chromophore (2.119 eV and 686.6 nm). Among all derivatives, SePTD2 exhibited some unique characteristics such as, least HOMO/LUMO energy gap (2.003 eV), highest absorption values (665.4 nm in gas and 724.2 nm in solvent), least binding energy (0.291 eV) and also significant value of open circuit voltage (1.860 V). The aforementioned findings suggest that employing molecular engineering with extended acceptors enhances the photovoltaic performance of non-fullerene materials, thereby encouraging experimentalists to develop highly efficient photovoltaic devices.

Benzoyl Valine Quasiracemates: Pairing CF3 Quasienantiomers with H to t-Butyl.

Understanding the interplay of structural features responsible for molecular assembly is essential for molecular crystal engineering. When assembling molecules with encoded motifs, first choice supramolecular strategies almost always include robust directional nonbonded contacts. Quasiracemic materials, considered near racemates since cocrystallization occurs with chemically unique components, lack a molecular framework or functional group restrictions, highlighting the importance of molecular shape to molecular assembly. Recently, our group reported quasiracemates derived from benzoyl leucine/phenylalanine derivatives with two points of chemical difference. In this study, we modified the chemical framework with valine and increased the scope of the work by imposing a larger variance in the side chain substituents. Pairing a CF3 component with quasienantiomers that differ iteratively from hydrogen to t-butyl offers an important view into the supramolecular landscape of these materials. Single-crystal X-ray crystallography and lattice energy assessments, coupled with conformational and crystal structure similarity searches, show an elevated degree of isomorphism for many of the targeted 17 racemates and quasiracemates. These benzoyl amino acid molecular architectures create extended hydrogen-bond patterns in the crystal that provide enhanced opportunities to study the shape space and molecular recognition profiles for a diverse family of quasienantiomeric components.

Molecular engineering of fluorescent dyes for long-term specific visualization of the plasma membrane based on alkyl-chain-regulated cell permeability

Long-term visualization of changes in plasma membrane dynamics during important physiological processes can provide intuitive and reliable information in a 4D mode. However, molecular tools that can visualize plasma membranes over extended periods are lacking due to the absence of effective design rules that can specifically track plasma membrane fluorescent dye molecules over time. Using plant plasma membranes as a model, we systematically investigated the effects of different alkyl chain lengths of FMR dye molecules on their performance in imaging plasma membranes. Our findings indicate that alkyl chain length can effectively regulate the permeability of dye molecules across plasma membranes. The study confirms that introducing medium-length alkyl chains improves the ability of dye molecules to target and anchor to plasma membranes, allowing for long-term imaging of plasma membranes. This provides useful design rules for creating dye molecules that enable long-term visualization of plasma membranes. Using the amphiphilic amino-styryl-pyridine fluorescent skeleton, we discovered that the inclusion of short alkyl chains facilitated rapid crossing of the plasma membrane by the dye molecules, resulting in staining of the cell nucleus and indicating improved cell permeability. Conversely, the inclusion of long alkyl chains hindered the crossing of the cell wall by the dye molecules, preventing staining of the cell membrane and demonstrating membrane impermeability to plant cells. The FMR dyes with medium-length alkyl chains rapidly crossed the cell wall, uniformly stained the cell membrane, and anchored to it for a long period without being transmembrane. This allowed for visualization and tracking of the morphological dynamics of the cell plasma membrane during water loss in a 4D mode. This suggests that the introduction of medium-length alkyl chains into amphiphilic fluorescent dyes can transform them from membrane-permeable fluorescent dyes to membrane-staining fluorescent dyes suitable for long-term imaging of the plasma membrane. In addition, we have successfully converted a membrane-impermeable fluorescent dye molecule into a membrane-staining fluorescent dye by introducing medium-length alkyl chains into the molecule. This molecular engineering of dye molecules with alkyl chains to regulate cell permeability provides a simple and effective design rule for long-term visualization of the plasma membrane, and a convenient and feasible means of chemical modification for efficient transmembrane transport of small molecule drugs.

Sterically Twisted Mitochondria‐Targeting Photosensitizers for Augmented Near‐Infrared II Fluorescence‐Guided Photodynamic Immunotherapy

AbstractNear‐infrared (NIR) fluorescent mitochondria‐targeting photosensitizers (PSs) hold great potential for efficient image‐guided cancer phototherapy, but it remains challenging to develop PSs concurrently integrating high‐contrast NIR‐II fluorescence imaging and efficient therapeutic capabilities. Herein, a heptamethine cyanine (HCy) PS (termed I2HCy‐TPE nanoparticles (NPs)) by a molecular engineering strategy combining the heavy atom effect and structural distortion is reported. The heavy atom iodine is introduced to boost the intersystem crossing process, and the bulky tetraphenylethylene (TPE) moiety placed at the meso‐position of the heptamethine chain creates a highly distorted conformation in I2HCy‐TPE, theoretically verified by density functional theory calculations. This strategy synergistically promotes the 1O2 generation efficiency and assure the strong NIR fluorescence emission in aggregated states. Combining with the intrinsic mitochondria‐targeting capability, I2HCy‐TPE NPs are able to cause mitochondria‐targeted damage of cancer cells via the PDT and immunogenetic cell death‐triggered immune responses under NIR laser irradiation. In vivo experiments demonstrate that the biocompatible I2HCy‐TPE NPs present exceptional capability for in vivo NIR‐II fluorescence bioimaging of whole‐body and blood vessels, and exert efficient NIR‐II fluorescence‐guided photodynamic immunotherapy against triple‐negative breast cancer.

Driving Triplet State Population in Benzothioxanthene Imide Dyes: Let's twist!

Controlling the formation of photoexcited triplet states is critical for many (photo)chemical and physical applications. Here, we demonstrate that a permanent out-of-plane distortion of the benzothioxanthene imide (BTI) dye promotes intersystem crossing by increasing spin-orbit coupling. This manipulation was achieved through a subtle chemical modification, specifically the bay-area methylation. Consequently, this simple yet efficient approach expands the catalog of known molecular engineering strategies for synthesizing heavy atom-free, dual redox-active, yet still emissive and synthetically accessible photosensitizers.

Molecular Engineering to Regulate the Pseudo-Graphitic Structure of Hard Carbon for Superior Sodium Energy Storage.

Resin-derived hard carbons have shown great advantages in serving as promising anode materials for sodium-ion batteries due to their flexible microstructure tunability. However, it remains a daunting challenge to rationally regulate the pseudo-graphitic crystallite and defect of hard carbon toward advanced sodium storage performance. Herein, a molecular engineering strategy is demonstrated to modulate the cross-linking degree of phenolic resin and thus optimize the microstructure of hard carbon. Remarkably, the resorcinol endows resin with a moderate cross-linking degree, which can finely tune the pseudo-graphitic structure with enlarged interlayer spacing and restricted surface defects. As a consequence, the optimal hard carbon delivers a notable reversible capacity of 334.3mAhg-1 at 0.02Ag-1, a high initial Coulombic efficiency of 82.1%, superior rate performance of 103.7mAhg-1 at 2Ag-1, and excellent cycling durability over 5000 cycles. Furthermore, kinetic analysis and in situ Raman spectroscopy are performed to reveal the electrochemical advantage and sodium storage mechanism. This study fundamentally sheds light on the molecular design of resin-based hard carbons to advance sodium energy for scale-up applications.

Elucidating Singlet-Fission-Born Multiexciton Dynamics via Molecular Engineering: A Dilution Principle Extended to Quintet Triplet Pair.

Multiexciton in singlet exciton fission represents a critical quantum state with significant implications for both solar cell applications and quantum information science. Two distinct fields of interest explore contrasting phenomena associated with the geminate triplet pair: one focusing on the persistence of long-lived correlation and the other emphasizing efficient decorrelation. Despite the pivotal nature of multiexciton processes, a comprehensive understanding of their dependence on the structural and spin properties of materials is currently lacking in experimental realizations. To address this gap in knowledge, molecular engineering was employed to modify the TIPS-tetracene structures, enabling an investigation of the structure-property relationships in spin-related multiexciton processes. In lieu of the time-resolved electron paramagnetic resonance technique, two time-resolved magneto-optical spectroscopies were implemented for quantitative analysis of spin-dependent multiexciton dynamics. The utilization of absorption and fluorescence signals as complementary optical readouts, in the presence of a magnetic field, provided crucial insights into geminate triplet pair dynamics. These insights encompassed the duration of multiexciton correlation and the involvement of the spin state in multiexciton decorrelation. Furthermore, simulations based on our kinetic models suggested a role for quintet dilution in multiexciton dynamics, surpassing the singlet dilution principle established by the Merrifield model. The integration of intricate model structures and time-resolved magneto-optical spectroscopies served to explicitly elucidate the interplay between structural and spin properties in multiexciton processes. This comprehensive approach not only contributes to the fundamental understanding of these processes but also aligns with and reinforces previous experimental studies of solid states and theoretical assessments.

Benzyl-methylbenzyl-benzene: Improving hydrogen storage and release performance of dibenzyltoluene based liquid organic hydrogen carrier

Liquid organic hydrogen carrier (LOHC) technology enables the safe, easy, and cost-effective storage and transportation of large quantities of hydrogen using inexpensive and mass-produced compounds. The LOHC materials play a crucial role in hydrogen storage capacity, reaction kinetics, reaction temperature, and reversibility. However, the development and optimization of LOHC materials is limited due to using of mass-produced materials for bulk hydrogen logistics. Herein, we propose a molecular engineering approach to overcome the limitations of commercial dibenzyltoluene (DBT)-based LOHC systems, considered one of the most promising LOHC materials based on the heat transfer oil, Marlotherm SH (MSH), owing to its superior physical properties (wide liquid range, and non-flammable properties), low price, and low toxicity. We devised a new chemical structure, benzyl-methylbenzyl-benzene (BMB), with highly improved dehydrogenation/hydrogenation performance achieved by rearranging the methyl group of DBT to overcome the limitations of slow reaction kinetics in terms of its chemical structure. The BMB exhibits a 150 % faster hydrogenation than MSH at 150 °C, and it releases 170 % more hydrogen compared to DBT at 270 °C. In addition, we analyzed the dehydrogenation/hydrogenation pathways according to the structures of DBT and BMB. Furthermore, we found that BMB (27 %) is inevitably generated in the MSH synthesis process alongside DBT (73 %). Based on this, we propose a streamlined and sustainable engineered method for improved MSH material manufacturing with a high BMB ratio (∼70 %). The scientific findings provide a fundamental understanding of DBT-based LOHC systems and new insights into the design of novel LOHC candidates.

Research Progress of β-Ketoenamine-Linked Covalent Organic Frameworks for Photocatalytic Hydrogen Evolution

β-Ketoamide covalent organic frameworks (COFs), also named Tp-COFs, are considered to be a milestone material in the history of photocatalysts because of their excellent visible-light absorption, high crystallinity, ultra-high stability and structural diversity. In recent years, a large number of Tp-COFs and their composites have been successfully constructed based on molecular or composite engineering strategies, and exhibited splendid photocatalytic water splitting activity. In comparison with a composite strategy, the molecular engineering technique effectively avoids interface problems by designing and preparing frameworks at the molecular level. Therefore, it is necessary to timely summarize the construction of Tp-COF photocatalysts based on the molecular engineering strategy, so as to provide some theoretical basis and enlightenment for the subsequent development of high-performance Tp-COFs. Finally, the shortcomings and challenges of this technique and personal views on the further development of Tp-COFs are presented.

Molecular Engineering of D‐π‐A Conjugate with N‐Heterocycle Purine for Enhanced ROS Generation and Photodynamic Therapy

AbstractThe efficient generation of reactive oxygen species (ROS) is crucial for the photodynamic therapy (PDT) effect. The D‐π‐A molecular engineering strategy can effectively separate the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) distribution to achieve a smaller energy gap thereby facilitating ROS generation of photosensitizers (PSs). Incorporating heterocycles as π‐bridges can not only extend the conjugation system with improving the degree of π‐delocalization but also effectively accelerate the intersystem crossing process. Herein, a N‐heterocycle purine is innovatively integrated into the D‐π‐A structure as a π‐bridge, which significantly enhances the photodynamic performance by achieving high levels of Type I and Type II ROS generation. The most potent TPM‐QN2 is obtained by modulating the electron‐withdrawing ability of the acceptor (quinolinium), with a 1O2 yield of 9.32, which is the highest yield reported to date. Furthermore, these purine‐based PSs exhibit excellent capabilities in promoting cell photodynamic ablation and inhibiting tumor tissue growth. This novel approach of introducing natural heterocycles provides a promising avenue for developing high‐performance PSs and promoting tumor phototherapy.

Near-Infrared Light-Driving Organic Photothermal Agents with an 88.9% Photothermal Conversion Efficiency for Image-Guided Synergistic Phototherapy.

Photothermal agents (PTAs) with desirable near-infrared (NIR) absorption and excellent photothermal conversion efficiency (PCE) are ideal candidates for cancer treatment. However, numerous PTAs still require high-intensity and long-duration laser irradiation to completely ablate the tumor during the photothermal therapy (PTT) process, resulting in light damage to healthy skin and tissue as well as limiting their biomedical applications. Integrating intense NIR absorption and high PCE into a single small-molecule PTA is an important prerequisite for realizing efficient PTT, but is a serious challenge. Herein, a series of donor-acceptor type PTAs (CC1 to NC4) are designed through a molecular engineering strategy. Theoretical calculations and experimental results show that the NIR absorption and photothermal effect from CC1 to NC4 are significantly enhanced as expected. Notably, NC4 nanoparticles exhibit intense NIR absorption, superhigh PCE of up to 88.9% for PTT, photoacoustic imaging and photothermal imaging, and effective reactive oxygen species generation for photodynamic therapy (PDT). The superior PTT/PDT synergistic phototherapeutic efficacy is well demonstrated by the complete elimination of tumor in vivo upon one-time, low-intensity, and short-duration laser irradiation (808nm, 330mW cm-2, and 3min). This work provides a valuable guideline for rational design of PTAs for cancer phototherapy.

Molecular engineering in tunable crystallinity of 2D covalent organic frameworks for efficient photocatalytic hydrogen evolution

The strategy of molecular engineering has been employed to build the structure–property–activity relationship for covalent organic frameworks (COFs) with efficient photocatalytic water splitting for hydrogen production. However, previous reports focus on the impact of molecular design on COFs’ physicochemical properties, the crystallinity differences are usually ignored and related studies remain rare. Herein, we describe the preparation of a series of structurally related COFs with similar chemical compositions but have different numbers of nitrogen (N) atoms in the central aromatic ring via an efficient crystallization strategy using of 2,4,6-triformyl resorcinol (TFR). On one hand, the introduction of N atoms reduces π-π stacking interaction during the formation of framework, leading to a decrease in crystallinity. On the other hand, it contributes to enhancing the photocatalytic performance of the materials by varying the electronic structures. Consequently, our results revealed that the photocatalytic hydrogen evolution (PHE) rate is 61.22 mmol g−1 h−1 for COF-905-1N, significantly higher than COF-905-3N (40.60 mmol g−1 h−1) and COF-905 (26.23 mmol g−1 h−1). This study not only provide fundamental insights into formation mechanism of COFs, but also provide a practical approach to enhance COF-based photocatalytic performance.

Molecular Engineering of Electrocatalytic Nanomaterials for Hydrogen Evolution: The Impact of Structural and Electronic Modifications of Anchoring Linkers on Electrocatalysis

Molecular Engineering of Electrocatalytic Nanomaterials for Hydrogen Evolution: The Impact of Structural and Electronic Modifications of Anchoring Linkers on Electrocatalysis

Molecular engineering of tetraphenylethene/thiophene-based donor/π-bridge units to enhance the AIE effect and boost the oxygen-independent type-I ROS generation

The development of oxygen-independent type-I photosensitizers (PSs) with aggregation-induced emission (AIE) characteristics is highly in demand to treat hypoxic tumors but remains challenging. In this contribution, three anion-π+ AIE-PSs (TPEMA-SI, TPEMA-SSI, and TPETPA-SSI) with strong donor-π-acceptor (D-π-A) configurations were facially synthesized by modulating donor/π-bridge units. The strength of D-π-A configurations as well as the AIE-effect that collectively promotes the intersystem crossing (ISC) for boosting the type-I ROS could be enhanced significantly by tuning the electronic characters of D/π-bridge units. The anion-π+ AIE-PSs, with strong D-π-A configurations and heavy atom effect, produced a mixture of type-I as well as type-II ROS. Among them, TPETPA-SSI, with strong D-π-A configuration as well as greater AIE-effect, demonstrated superior type-I ROS generation efficiency. The biocompatible nanoparticles of anion-π+ AIE-PSs (AIE-PSs NPs) were fabricated after being encapsulated into an amphiphilic polymer (DSPE-PEG). The TPETPA-SSI NPs with superior ROS generation efficiency, demonstrate efficient PDT effects towards MCF-7 and U87MG cancer cells in both normoxia and hypoxia environments. This study provides insights into the design and development of type-I AIE-PSs by enhancing the strength of D-π-A configurations and the AIE effect

Molecular Engineering toward Broad Color‐Tunable Emission of Pyrene‐Based Aggregation‐Induced Emission Luminogens

AbstractA molecular design strategy for the precise regulation of full‐color‐tunable emission organic luminescence materials is not yet systematically established for pyrene chemistry. To fabricate color‐tunable and highly‐efficiency pyrene‐based emitters, this article presents novel pyrene‐based molecules with donating‐π‐accepting structures, which exhibit bright, relatively narrow‐band FWHM emission, broad color‐tunable from deep blue (439 nm) to orange‐red (599 nm) both in solution and in the solid state. Moreover, the compounds 2a, 2d–g exhibit typical aggregation‐induced emission (AIE) characteristics, with an enhanced fluorescence quantum yield in the solid state. The experimental results indicated that the presence of the sterically bulky meta‐substituted biphenyl adopts an out‐of‐plane twist conformation, which can strengthen the rigidity of the molecular conformation and suppress the intermolecular π–π stacking in the aggregated state, resulting in an enhanced emission in the solid state. The prepared pyrene‐based AIEgens are applied as fluorescent inks to write Chinese characters and art with a vivid pattern. Thus, this article not only presents an efficient molecular strategy to construct pyrene‐based AIEgen with broad color‐tunable emission properties for practical applications, but also display a powerful combination of the strong alliance between the advanced luminescent materials, art and Chinese traditional culture.

Improved the optical nonlinearity of carbazole based chromophores via molecular engineering: A DFT approach

The present investigation was based on designing of carbazole based derivatives (DTCFD1–DTCFD8) having D1-π-D2-π-A architecture from DTCFR, upon substituting acceptor motifs for nonlinear optical (NLO) materials. M06-2X/6-311G(d,p) level was accomplished to explore the optoelectronic behavior of designed compounds. The UV–Vis, density of states (DOS), natural bond orbitals (NBOs), transition density matrix (TDM) and frontier molecular orbitals (FMOs) analyses were executed to comprehend the nonlinear optical properties of above-mentioned compounds. The FMO analysis showed DTCFD7 as having the lowest energy gap at 3.734 eV among the derivatives, indicating its potential for efficient charge transfer. The overall decreasing order of band gaps was observed: DTCFR > DTCFD5 > DTCFD3 > DTCFD1 > DTCFD2 > DTCFD4 > DTCFD6 > DTCFD7. UV–Visible analysis exploited that DTCFD7 displayed distinctive absorption characteristics. In the gas phase, it exhibited a λmax of 494.927 nm, while in the dichloromethane it showed a significantly higher λmax of 516.515 nm, then all other derivatives. All the derivatives exhibited greater values of linear polarizability [〈α〉=1.633–1.786 × 10−22esu], first hyperpolarizability (βtot = 3.690–6.549 × 10−28esu) and second hyperpolarizability (γtot = 4.825–7.229 × 10−33esu) as compared to the reference molecule. Furthermore, NLO analysis revealed that the highest βtot (6.549 × 10−28esu) and γtot (7.229 × 10−33esu) was exhibited by DTCFD7 and DTCFD1, respectively, then other derivatives. Moreover, a comparative study with standard urea and para-nitroaniline (p-NA), exhibited effective NLO properties in current study compounds. In light of the comprehensive findings, this study concludes that the designed compounds may be considered as effective NLO materials.