A novel method for interfacial energy gap determination.

A precise quantification of energy gap for a molecular semiconductor is crucial. However, there has always been a lack of a suitable method which results in an inaccurate measurement. In this research, a three-terminal vertical structure (Al/AlOX/Au/ molecular semiconductor/Al), named hot electron transistor has been designed to be the most powerful method for energy gap determination. By analysing the IC-hot-VEB curves, the electron injected barrier and hole injected barrier can be extracted. In combination of the both, the energy gap of four objects, including PBDB-T-2Cl, C60, PTCDA, and Alq3, has been determined finally.

Structural and Optical Characterization of Porous NiV2O6 Films Synthesized by Nebulizer Spray Pyrolysis for Photodetector Applications.

NiV2O6 thin films were grown on glass slides with varying thicknesses using nebulizer spray pyrolysis. The impact of thickness on the thin films' optical, structural, morphological, and electrical characteristics was systematically investigated. X-ray diffraction and micro-Raman analysis confirmed the formation of the triclinic NiV2O6 system. Surface morphology and roughness variations in the as-deposited NiV2O6 films were studied using scanning electron microscopy (SEM) and a profilometer. Optical properties, including optical band gap (Eg), extinction coefficient (k), absorption coefficient (α), and refractive index (n), were determined through optical reflectance and transmittance measurements. The optical energy gap of the as-deposited NiV2O6 films decreased from 2.02 eV to 1.58 eV with increased layer thickness. Furthermore, the photo-detectivity of the films demonstrated an enhancement corresponding to the prolonged spray time. The sensitivity values obtained for visible irradiation were 328, 511, and 433 for samples S1, S2, and S3, respectively. The obtained results can be imputed to the specific porous microstructure.

Theoretical, structural, and electronic analyses of pyridin-based dyes for dye-sensitized solar cells applications.

CONTEXT: The new series of donor-π-acceptor dyes have been designed using pyridine derivatives as a donor group and thienothiophene as a π-spacer group, which were linked via 10 acceptor groups. The highest occupied molecular orbital energies range from - 6.177 to - 5.786 eV, whereas the lowest unoccupied molecular orbital energies range from - 2.181 to - 3.664 eV. A6 dye has smaller energy gap, lower hardness, higher electrophilicity index, and good photovoltaic performance than other sensitizers. The lowest dihedral angle is observed in A1, A2, A6, A7, and A8 which are appropriate for intramolecular charge transfer between the molecules. The A8 has higher light harvesting efficiency, which increases the photovoltaic efficiency of the designed dye. The A6, A7, and A8 dyes spend less time in the excited state, which means they emit photons more efficiently than other dyes. The interaction between donor to π-spacer (red line) parts of the dyes has the bonding interaction (positive), and π-spacer to acceptor (blue line) parts of the dyes have the bonding and antibonding (negative) behaviours. The dyes A5 and A9 have 305.79 and 357.71 times higher ß0 values than urea (0.781 × 10-30 esu) molecules. The spectral properties of the A6 dye strongly affect the structural modification. METHODS: The density functional theory (DFT) and time-dependent DFT (TD-DFT) approach B3LYP/6-311G (d,p) basic set were used to optimize the designed dyes. All the calculations are performed using Gauss view 6.0 and Gaussian 09 software. The density of state spectrum is plotted using Gauss sum 2.6.

The enhanced photocatalytic performance of CPAA doping with different concentrations of Titanium oxide nanocomposite against MB dyes under simulated sunlight irradiations.

The pure conjugated polyarylene azomethine (CPAA) and its nanocomposites (CPAA-TiO2) with different concentrations of TiO2 nanoparticles were successfully prepared by in-situ technique and analyzed by different advanced techniques. XRD has confirmed the structural properties and crystallinity of (CPAA) and nanocomposites. The SEM clearly shows that the (CPAA) is uniform and homogeneous, with tightly connected aggregate layers in shape. However, the amount of TiO2 in the nanocomposites greatly affects their morphology, revealing structural differences and indicating a reaction between (CPAA) and TiO2, especially at a higher concentration of 5% TiO2. A new composite of (CPAA) was introduced and the photocatalytic effect for MB was studied. The removal efficiency of (pure-CPAA) over MB dye under simulated sunlight was 62%. However, (CPAA-TiO2 1%) destroyed 90% of MB dyes. It was discovered that the low band gap of (CPAA-TiO2 1% (2.84 eV)) accelerates high electron-hole recombination, increasing photocatalytic activity.

Energy gap and aromatic molecular rings.

The manuscript combines rational density functional theory simulations and experimental data to investigate the electrical properties of eight polycyclic aromatic hydrocarbons (PAHs). The optimized geometries reveal a preference for one-row, two-row and three-row ring distributions. Band structure plots demonstrate an inverse correlation between the number of aromatic rings and band gap size, with a specific order observed across the PAHs. Gas phase simulations support these findings, though differences in values are noted compared to the literature. Introducing a two-row ring distribution concept resolves discrepancies, particularly in azulene. The B3LYP function successfully bridges theoretical and experimental gaps, particularly in large PAHs. The manuscript highlights the potential for designing electronic devices based on different-sized PAHs, emphasizing a multi-ring distribution approach and opening new avenues for practical applications.

Energy difference-driven ROS reduction for electrochemical tracking crop growth sensitized with electron-migration nanostructures.

Aiming for sustainable crop productivity under changing climate conditions, it is essential to develop handy models for in-situ monitoring of reactive oxygen species (ROS). Herein, this work reports a simple electrochemical sensing toward hydrogen peroxide (H2O2) for tracking crop growth status sensitized with electron-migration nanostructure. To be specific, Cu-based metal-organic frameworks (MOFs) with high HOMO energy level are designed for H2O2 reduction on account of Cu(I)/Cu(II) redox switchability. Importantly, the sensing performance is improved by electrochemically reduced graphene oxide (GO) with ready to use feature. To overcome the shortcomings of traditional liquid electrolytes, conductive hydrogel as semi-solid electrolyte exhibits the adhesive property to the cut plant petiole surface. Benefitting from the preferred composite models and conductive hydrogel, the electrochemical sensing toward H2O2 with high sensitivity and good anti-interference against the coexistent molecules, well qualified for acquiring plant growth status.

The high impact of zinc chromium oxide nanocombs on development of larvicidal and antimicrobial performance.

Zinc chromium oxide (Cr/ZnO, 5wt.%) was prepared by a facile chemical co-precipitation route. The structure, composition, and chemical bonding were analyzed using X-ray diffraction (XRD), Energy dispersive X-ray spectroscopy (EDX), and Fourier-transform infrared spectroscopy (FTIR) indicating that chromium ions were integrated the host framework to form Cr/ZnO nanocomposite. Scanning electron microscopy (SEM) and Transmission electron microscopy (TEM) micrographs showed comb-shaped nanoparticles with an average size 20 nm and large surface area. The energy gap of the thin films was estimated from T% and R% measurements which exhibit a strong optical absorption edge close to the visible spectrum. The insecticidal activity of the synthesized nanocombs against C. pipiens larvae was evaluated with LC50 (30.15 ppm) and LC90 (100.22 ppm). Besides, the nanocomposite showed high antibacterial performance against gram-positive bacteria (Bacillus subtilis) and gram-negative bacteria (Proteus vulgaris) with inhibition zones 21.9 and 19 mm, respectively.

Exploration of high-performance triptycene-based thermally activated delayed fluorescence materials via structural alteration of donor fragment.

The utilization of thermally activated delayed fluorescence (TADF) materials in highly proficient organic light-emitting diodes (OLEDs) has attracted much attention. Based on TADF material TPA-QNX(CN)2, a series of three-dimensional donor-acceptor (D-A) triptycenes have been designed via structural modification of D-fragment. The influences of different D-fragments with various electron-donating strengths on the singlet-triplet energy gap (ΔEST), emission wavelength (λem), and electron/hole reorganization energy (λe/λh) are extensively studied by applying density functional theory (DFT) coupled with time-dependent density functional theory (TD-DFT). The computed results imply that as the electron-donating strength of the D-fragments increases, the ΔEST value decreases and λem is red-shifted for the molecules using the same acceptor units. Analogously, the 1CT‒3CT state splitting (ΔEST (CT)) is also decreased by enlarging the twist angle (ß) between the phenyl ring and alternative D-fragment. Therefore, efficient color tuning within a broad emission range (434-610 nm), as well as small ΔEST (CT) values (0.01-0.05 eV), has been accomplished by structural modification of the D-fragments. The greater electron-donating strength, the smaller ΔEST, and the smaller λh for PPXZ-QNX(CN)2 make it the best candidate among all the designed molecules.

The chemical recognition of hydrogen fluoride via B24N24 nanocage: quantum chemical approach.

CONTEXT: Ab initio calculations were employed in this investigation to scrutinize the adsorption characteristics of a linear chain (HF)n on a BN nanocage (B24N24), wherein the chain lengths varied (n = 1, 2, 3, and 4). The overarching aim was to assess the efficiency of this setup in detecting and adhering to (HF)n under both liquid and gaseous scenarios. This study encompassed an array of aspects, encompassing adsorption energy, optimal configuration determination, work function analysis, and charge exchange assessment. Furthermore, an exploration was conducted into the impact of HF linear chain dimensions on electrical attributes and adsorption energy. According to the values of adsorption energy, the dimer form of HF adsorbed onto BN nanocages displayed the highest stability. METHODS: This scrutiny was undertaken utilizing density functional theory (DFT), employing the B3LYP functional and the 6-31 + + G(d,p) basis set. Notably, the choice of the 6-31 + + G(d,p) basis set is particularly apt for delving into nanostructure analyses. The HOMO-LUMO energy gap was significantly reduced by (HF)n upon adsorption onto the nanocage, falling from 6.48 to 5.43 eV and enhancing electrical conductivity as a result. Additionally, BN nanocages may be used as sensors to find (HF)n among other environmental pollutants.

Enhancement of Ni-Zn ferrite nanoparticles parameters via cerium element for optoelectronic and energy applications.

This work is concerned with fabricating ferrite nanoparticles of nickel-zinc with the chemical formula: Ni0.55Zn0.45Fe2-xCexO4, 0 ≤ x ≤ 0.011 by co-deposition technique and modifying their electrical, microscopic, spectroscopic, optical, electrical and dielectric properties as advanced engineering materials through doping with the cerium (Ce) element. XRD patterns displayed that the samples have a monophasic Cerium-Nickel-zinc (CNZ) spinel structure without other impurities for cerium concentration (x) ≤ 0.066. Both values of crystallite size and lattice parameters decrease from 33.643 to 23.137 nm and from 8.385 to 8.353 nm, respectively, with the increasing Ce ions substitution content from 0 to 0.066. SEM images indicate that grains of the fabricated compounds are smaller, more perfect, more homogeneous, and less agglomeration than those of the un-doped Ni-Zn nano-ferrites. The maximum intensity of first-order Raman spectral peaks (Eg, F2g(2), A1g(2), and A1g(1)) of CNZ ferrite nanoparticles are observed at about (330, 475, 650, 695) cm-1, respectively, that confirms the CNZ samples have the cubic spinel structure. The direct and indirect optical energy bandgaps of CNZ samples have a wide spectrum of values from semiconductors to insulators according to cerium concentration. The results showed that the values of dielectric constant, dielectric loss factor, and Ac conductivity and the conductivity transition temperature are sensitive to cerium ions content. AC conductivity exhibited by the CNZ samples has the semiconductor materials behavior, where the AC conductivity increases due to temperature or doping concentration. The results indicate that Ni0.55Zn0.45Fe1.944Ce0.066O4 ferrite nanoparticles may be selected for optoelectronic devices, high-frequency circuits, and energy storage applications.

Exploration of violet-to-blue thermally activated delayed fluorescence emitters based on "CH/N" and "H/CN" substitutions at diphenylsulphone acceptor. A DFT study.

The violet-to-blue thermally activated delayed fluorescence (TADF) emitters were created employing several substituents based on 5,5-dimethyl-5,10-dihydropyrido [2,3-b][1,8] naphthyridine-diphenylsulphone (DMDHPN-DPS) called 1a via "CH/N" and "H/CN" substitutions at the diphenylsulphone acceptor (DPS) moiety. The parent compound 1a was selected from our former work after extensive research employing "CH/N" substitution on Dimethyl-acridine (DMAC) donor moiety. There is a little overlap amid the highest occupied molecular orbitals (HOMOs) and lowest un-occupied molecular orbitals (LUMOs) due to the distribution of HOMOs and LUMOs primarily on the DMDHPN donor and the DPS acceptor moieties, respectively. It resulted in a narrower energy gap (∆E ST) between the lowest singlet (S1) and triplet (T1) excited state. In nearly all derivatives, the steric hindrance results in a larger torsional angle (85°-98°) between the plane of the DMDHPN and the DPS moieties. The predicted ΔE ST values of the compounds with "H/CN" substitution were lower than those of the comparable "CH/N" substituents, demonstrating the superiority of the reversible inter-system crossing (RISC) from the T1 → S1 state. All derivatives have emission wavelengths (λ em) in the range of 357-449 nm. The LUMO → HOMO transition energies in the S1 states are lowered by the presence of -CN groups or -N = atoms at the ortho or meta sites of a DPS acceptor unit, causing the λ em values to red-shift. Furthermore, the λ em showed a greater red-shift as there were more-CN groups or -N = atoms. Three of the derivatives named 1b, 1g, and 1h, emit violet (394 nm, 399 nm, and 398 nm, respectively), while two others, 1f and 1i, emit blue shade (449 nm each) with reasonable emission intensity peak demonstrating that these derivatives are effective violet-to-blue TADF nominees. The lower ΔE ST value for derivative 1i (0.01 eV) with λ em values of 449 nm make this molecule the finest choice for blue TADF emitter amongst all the studied derivatives. We believe our research might lead to the development of more proficient blue TADF-OLEDs in the future.

Correlation of Broad Absorption Band with Small Singlet-Triplet Energy Gap in Organic Photovoltaics.

Organic photovoltaics (OPV) are one of the most effective ways to harvest renewable solar energy, with the power conversion efficiency (PCE) of the devices soaring above 19 % when processed with halogenated solvents. The superior photocurrent of OPV over other emerging photovoltaics offers more opportunities to further improve the efficiency. Tailoring the absorption band of photoactive materials is an effective way to further enhance OPV photocurrent. However, the field has mostly been focusing on improving the near-infrared region photo-response, with the absorption shoulders in short-wavelength region (SWR) usually being neglected. Herein, by developing a series of non-fullerene acceptors (NFAs) with varied side-group conjugations, we observe an enhanced SWR absorption band with increased side-group conjugation length. The underpinning factors of how molecular structures and geometries improve SWR absorption are clearly elucidated through theoretical modelling and crystallography. Moreover, a clear relationship between the enhanced SWR absorption and reduced singlet-triplet energy gap is established, both of which are favorable for the OPV performance and can be tailored by rational structure design of NFAs. Finally, the rationally designed NFA, BO-TTBr, affords a decent PCE of 18.5 % when processed with a non-halogenated green solvent.

Unveiling the Noncovalent Interaction of Thiazol-2-ylidene and Its Derivatives as N-heterocyclic Carbene with Different Proton Donor Molecules.

The importance of noncovalent interaction has gained attention in various domains covering drug and novel catalyst design. The present study mainly characterizes the role of hydrogen bond (H-bond) and other intermolecular interactions in different (1 : 1) complex analogues formed between the N-aryl-thiazol-2-ylidene (YR) and five proton donor (HX) molecules. The analysis of the singlet-triplet energy gap ( Δ E S - T ${{\rm{\Delta }}E_{\left( {S - T} \right)} }$ ) confirmed the stability of the singlet state for this class of N-aryl-thiazol-2-ylidenes than the triplet state. The interaction energy values of the YR-HX complexes follow the order: YR-NH3

Molecular design of D-π-A-π-D small molecule donor materials with narrow energy gap for organic solar cells applications.

CONTEXT: Developing novel materials present a great challenge to improve the photovoltaic performance of organic solar cells (OSCs). In this paper, we designed a series of the donor-π bridge-acceptor-π bridge-donor (D-π-A-π-D) structure molecules. These molecules consist of diketopyrrolopyrrole (DPP) moiety as core, 9-hexyl-carbazole moiety as terminal groups, and different planar electron-rich aromatic groups as π-bridges. The density functional theory (DFT) and time-dependent DFT (TD-DFT) computations showed that the frontier molecular orbital (FMO) energy levels, energy gaps, electron-driving forces (ΔEL-L), open-circuit voltage (Voc), fill factor (FF), reorganization energy (λ), exciton binding energy (Eb), and absorption spectra of the designed molecules can be effectively adjusted by the introduction of different π-bridges. The designed molecules have narrow energy gap and strong absorption spectra, which are beneficial for improving the photoelectric conversion efficiency of organic solar cells. In addition, the designed molecules possess large ΔEL-L, large Voc, and FF values and low Eb when the typical fullerene derivatives are used as acceptors. The FMO energy levels of the designed molecules can provide match well with the typical fullerene acceptors PC61BM, bisPC61BM, and PC71BM. Our results suggest that the designed molecules are expected to be promising donor materials for OSCs. METHODS: All DFT and TD-DFT calculations were carried out using the Gaussian 09 code. The computational technique chosen was the hybrid functional B3LYP and the 6-31G(d,p) basis set. The benzene and chloroform solvent effects have been considered using the polarized continuum model (PCM) at the TD-DFT level. The simulated absorption spectra of designed molecules were plotted by using the GaussSum 1.0 program.

Integration of ZnO nanorods with silver ions by a facile co-precipitation for antimicrobial, larvicidal, and ovicidal activity.

BACKGROUND: Infectious diseases prompted by micro-organisms such as fungi, parasites, or microbes, have influenced many countries' public health causing death. Scientists declared that metal oxide composites have various advantages in the medical field such as the antimicrobial feature has freshly been revealed as well as its role in suppressing mosquito population. METHODS: In this work silver doped zinc oxide nanorods (Ag/ZnO NRs, 10 wt.%) were prepared by simple chemical route, and their microstructural characteristics were investigated by XRD, EDX, SEM, and TEM techniques. The antimicrobial, larvicidal, and ovicidal of the synthesized nanocomposites were examined. RESULTS: The synthesized nanocomposite exhibited binary phase of crystallite size 112 nm was calculated from Williamson-Hall method. EDX spectrum revealed the purity of the composite consists of Zn, O, and Ag elements. The SEM and TEM micrographs showed the particles in nanorods with high density on the surface. The energy gap [Formula: see text] was evaluated from the UV-Vis absorbance in the range from 2.90 [Formula: see text] 3.08 eV inside the visible spectrum. The antimicrobial activity of the nanorods was examined against Gram-positive bacteria (Staphylococcus aureus and Bacillus subtilis) with inhibition zones 10.5 and 14.5 mm, respectively. Whereas gram-negative bacteria (Escherichia coli, Salmonella Typhimurium, and Pseudomonas aeruginosa) were 14 and 17 mm, respectively. Further, Candida albicans was investigated with inhibition zone 7.5 mm. Besides, the insecticidal impact of the nanocomposite against Culex pipiens larvae was performed at 30 mg/l causing 100% larval mortality with LC50 (11.78 mg/l). The micrograph images showed deformations in the larval body as well as egg resulting in zero egg hatchability. CONCLUSION: The findings approved that synthesized nanorods have a significant impact on controlling pathogens that impart different diseases to humans and the environment.

A computational study of CuCrX2 (X = S, Se, Te) for intermediate band solar cell: Conceptual density functional theory approach.

Transition metals doped semiconductors have been extensively used as a greener alternative to lead-based solar cell materials. In this work, we have investigated the structure, electronic, optical, and thermo-chemical properties of CuCrX2 (X = S, Se, Te) by using the Conceptual Density Functional Theory (CDFT) approach. Different suitable exchange correlations have been used for the process of geometry optimization of systems in the study. Applied exchange correlations namely B3LYP and WB97XD demonstrate that the energy gap shows a decline from the atom S to Se to Te. HOMO-LUMO obtained from level B3LYP/LANL2DZ is in accordance with the stated data. The attained band gap directs that studied materials could be beneficial for further utilization in optoelectronic and photovoltaic devices. A comparative study has been made based on the selected exchange correlations for the analysis of investigated materials, which has not been explored commonly. The study reveals that B3LYP/LANL2DZ could be a better choice for a combination set of level and basis set for studying these types of compounds. CDFT-based global reactivity descriptors are computed and analyzed. The obtained band gap range indicates the desirable nature of CuCrX2 for further exploration in the application of Intermediate Band Solar cells.

Excited-State Dynamics of All the Mono-cis and the Major Di-cis Isomers of ß-Apo-8'-Carotenal as Revealed by Femtosecond Time-Resolved Transient Absorption Spectroscopy.

Cis isomers of carotenoids play important roles in light harvesting and photoprotection in photosynthetic bacteria, such as the reaction center in purple bacteria and the photosynthetic apparatus in cyanobacteria. Carotenoids containing carbonyl groups are involved in efficient energy transfer to chlorophyll in light-harvesting complexes, and their intramolecular charge-transfer (ICT) excited states are known to be important for this process. Previous studies, using ultrafast laser spectroscopy, have focused on the central-cis isomer of carbonyl-containing carotenoids, revealing that the ICT excited state is stabilized in polar environments. However, the relationship between the cis isomer structure and the ICT excited state has remained unresolved. In this study, we performed steady-state absorption and femtosecond time-resolved absorption spectroscopy on nine geometric isomers (7-cis, 9-cis, 13-cis, 15-cis, 13'-cis, 9,13'-cis, 9,13-cis, 13,13'-cis, and all-trans) of ß-apo-8'-carotenal, whose structures are well-defined, and discovered correlations between the decay rate constant of the S1 excited state and the S0-S1 energy gap, as well as between the position of the cis-bend and the degree of stabilization of the ICT excited state. Our results demonstrate that the ICT excited state is stabilized in polar environments in cis isomers of carbonyl-containing carotenoids and suggest that the position of the cis-bend plays an important role in the stabilization of the excited state.

Identification and sensing of hydrogen fluoride (HF) on aluminum phosphide (Al24P24) nanocage in both gas and water phases: electronic study via density-functional theory computations.

CONTEXT: Hydrogen fluoride (HF) is extensively present in environmental and industrial pollutants. It may harm the health of humans and animals. This work evaluated the adsorption of an (HF)n linear chain (n = 1, 2, 3, and 4) onto an AlP nanocage through ab initio calculations for the evaluation of its performance in sensing and monitoring (HF)n within aqueous and gaseous media. METHODS: The present work adopted density functional theory (DFT) at the 6-311 G (d, p) basis set to analyze (HF)n linear chain adsorption onto AlP nanocages with the B3LYP functional. This paper examined the adsorption energy, configuration optimization, work function, and charge transfer. In addition, the contributions of the HF linear chain size to electronic properties and adsorption energy were measured. The dimer form of HF on the surface of AlP nanocages was found to have the highest stability based on the adsorption energy values. Once (HF)n was adsorbed onto the nanocage, the HOMO-LUMO energy gap experienced a large reduction from 3.87 to 3.03 eV, enhancing electrical conductivity. In addition, AlP nanocages may serve in the sensing of (HF)n under multiple environmental pollutants.

Balanced Energy Gaps as a Key Design Rule for Solution-Phase Organic Room Temperature Phosphorescence.

Metal-free organic emitters that display solution-phase room temperature phosphorescence (sRTP) remain exceedingly rare. Here, we investigate the structural and photophysical properties that support sRTP by comparing a recently reported sRTP compound (BTaz-Th-PXZ) to two novel analogous materials, replacing the donor group by either acridine or phenothiazine. The emissive triplet excited state remains fixed in all three cases, while the emissive charge-transfer singlet states (and the calculated paired charge-transfer T2 state) vary with the donor unit. While all three materials show dominant RTP in film, in solution different singlet-triplet and triplet-triplet energy gaps give rise to triplet-triplet annihilation followed by weak sRTP for the new compounds, compared to dominant sRTP throughout for the original PXZ material. Engineering both the sRTP state and higher charge-transfer states therefore emerges as a crucial element in designing emitters capable of sRTP.

Bathochromic Shift of Fluorescence Peak in Dipyrrolo[1,2-a:2',1'-c]quinoxaline by Introducing Each of Electron-Donating and Electron-Withdrawing Substituent.

Development of organic fluorophore is an important theme. Especially, the fluorophores with longer fluorescence peaks are useful to biological probes. One of the methods to change the fluorescence peak is the introduction of substituents. However, opposing characteristics of the substituents lead to different changes in the fluorescence peaks. Furthermore, the introduction of the substituent also affects their electric properties. Thus, if the materials were developed with the substituent effect on the optical and electric properties separately, it will be useful to design the functional materials related to both optical and electric properties. Herein, we investigated the substituent effect of dipyrrolo[1,2-a:2',1'-c]quinoxalines on fluorescence properties. We synthesized the compounds bearing electron-donating or electron-withdrawing substituents at the benzene ring on dipyrrolo[1,2-a:2',1'-c]quinoxaline, which would have more direct influence on the optical properties. By introducing each substituent at the 6 position of dipyrrolo[1,2-a:2',1'-c]quinoxaline, the bathochromic shift was observed in the fluorescence spectra. In the case of fluorine substituent, the change of the fluorescence peak reached was about 19 nm. Using a TDDFT calculation, we explained the reason for such a substituent effect that large on the increment of LUMO energy or decrement of HOMO energy occurred by introducing electron-withdrawing or electron-donating substituents at the 6 position, respectively. The substituent effect on the change of orbital energies is typical although the different characteristics of substituents resulted in the similar tendency about the change of fluorescence peak. Furthermore, with the introduction of phenyl substituents at the 3 and 10 positions, we achieved 40-50 nm longer fluorescence peaks compared with that of the original dipyrrolo[1,2-a:2',1'-c]quinoxaline.