Photophysical properties of donor (D)-acceptor (A)-donor (D) diketopyrrolopyrrole (A) systems as donors for applications to organic electronic devices.

Fourteen substituted diketopyrrolopyrrole (DPP) molecules in a donor (D)-acceptor (DPP)-donor (D) arrangement were designed. We employed density functional theory, time-dependent DFT, DFT-MRCI and the ab initio wave function second-order algebraic diagrammatic construction (ADC(2)) methods to investigate theoretically these systems. The examined aromatic substituents have one, two, or three hetero- and non-hetero rings. We comprehensively investigated their optical, electronic, and charge transport properties to evaluate potential applications in organic electronic devices. We found that the donor substituents based on one, two, or three aromatic rings bonded to the DPP core can improve the efficiency of an organic solar cell by fine-tuning the highest occupied molecular orbital/lowest unoccupied molecular orbital levels to match acceptors in typical bulk heterojunctions acceptors. Several properties of interest for organic photovoltaic devices were computed. We show that the investigated molecules are promising for applications as donor materials when combined with typical acceptors in bulk heterojunctions because they have appreciable energy conversion efficiencies resulting from their low ionization potentials and high electron affinities. This scenario allows a more effective charge separation and reduces the recombination rates. A comprehensive charge transfer analysis shows that D-A (DDP)-D systems have significant intramolecular charge transfer, further confirming their promise as candidates for donor materials in solar cells. The significant photophysical properties of DPP derivatives, including the high fluorescence emission, also allow these materials to be used in organic light-emitting diodes.

Ab initio electronic absorption spectra of para-nitroaniline in different solvents: Intramolecular charge transfer effects.

Intramolecular charge transfer (ICT) effects of para-nitroaniline (pNA) in eight solvents (cyclohexane, toluene, acetic acid, dichloroethane, acetone, acetonitrile, dimethylsulfoxide, and water) are investigated extensively. The second-order algebraic diagrammatic construction, ADC(2), ab initio wave function is employed with the COSMO implicit and discrete multiscale solvation methods. We found a decreasing amine group torsion angle with increased solvent polarity and a linear correlation between the polarity and ADC(2) transition energies. The first absorption band involves π → π* transitions with ICT from the amine and the benzene ring to the nitro group, increased by 4%-11% for different solvation models of water compared to the vacuum. A second band of pNA is characterized for the first time. This band is primarily a local excitation on the nitro group, including some ICT from the amine group to the benzene ring that decreases with the solvent polarity. For cyclohexane, the COSMO implicit solvent model shows the best agreement with the experiment, while the explicit model has the best agreement for water.

Design of 2-Pyridone Fluorophores for Brighter Emissions at Longer Wavelengths.

The recent discovery of blue fluorophores with high quantum yields based on pyridone structures inspired the development of new low-molecular-weight fluorophores with bright emissions at tunable wavelengths, which are highly attractive for various applications. In this study, we propose a rational design strategy for 2-pyridone-based fluorophores with bright emissions at long wavelengths. With a detailed understanding of the positional substitution effects on each carbon atom of the 2-pyridone core, we developed a bright blue fluorophore (λabs =377 nm; λem =433 nm; ϵ=13,200 M-1 cm-1 ; ϕF =88 %) through C3 -aryl and C4 -ester substitutions followed by cyclization. Furthermore, by applying the intramolecular charge transfer (ICT) principle, we invented a bright green fluorophore through C3 - and C4 -diester and C6 -aryl substitutions. The ICT fluorophore based on the pyridone structure shows large molar absorptivity (ϵ=20,100 M-1 cm-1 ), longer emission wavelength (λem =539 nm), high emission quantum yield (ϕF =74 %), and large Stokes shift (Δv=5720 cm-1 ), which are comparable to those of practical fluorescent probes.

Tuning the Photophysical Properties of Aza-BODIPYs in the Near-Infrared Region by Introducing Electron-Donating Thiophene Substituents.

This study presents the synthesis, the spectroscopic and electrochemical properties of new bis- and tetra-substituted azaboron-dipyrromethene (aza-BODIPY) dyes substituted by different electron donating groups connected to the aza-BODIPY core through a thiophene unit. In line with theoretical calculations, experimental measurements point out the positive impact of the thiophene group that behave as a secondary donor group leading to an enhancement of the intramolecular charge transfer process in comparison to previously reported aza-BODIPY dyes. This heterocycle has also been found to tune the oxidative potential and to stabilize the electro-generated species.

Tunable Fluorescence via Self-Assembled Switching of AIE-Active Micelle-like Nanoaggregates.

Chemical structures bearing a combination of aggregation-induced emission enhancement (AIEE) and intramolecular charge transfer (ICT) properties attracted the attention of many researchers. Recently, there is an increasing demand to pose tunable AIEE and ICT fluorophores that could present their conformation changes-related emission colors by adjusting the medium polarity. In this study, we designed and synthesized a series of 4-alkoxyphenyl-substituted 1,8-naphthalic anhydride derivatives NAxC using the Suzuki coupling reaction to construct donor-acceptor (D-A)-type fluorophores with alkoxyl substituents of varying carbon chain lengths (x = 1, 2, 4, 6, 12 in NAxC). To explain the observation that molecules with longer carbon chains revealed unusual fluorescence enhancement in water, we study the optical properties and evaluate their locally excited (LE) and ICT states by solvent effects combined with Lippert-Mataga plots. Then, we explored the self-assembly abilities of these molecules in water-organic (W/O) mixed solutions and observed the morphology of its nanostructure using a fluorescence microscope and SEM. The results show that NAxC, x = 4, 6, 12 show different degrees of self-assembly behaviors and corresponding aggregation-induced emission enhancement (AIEE) progresses. At the same time, different nanostructures and corresponding spectral changes can be obtained by adjusting the water ratio in the mixed solution. That is, NAxC compounds present different transitions between LE, ICT and AIEE based on the polarity, water ratio and time changes. We designed NAxC as the structure-activity relationship (SAR) of the surfactant to demonstrate that AIEE comes from the formation of micelle-like nanoaggregates, which causes a restriction of the transfer from the LE state to the ICT state, and micelle formation results in a blue-shift in emission and enhances the intensity in the aggregate state. Among them, NA12C is most likely to form micelles and the most obvious fluorescence enhancement, which will switch over time due to the nano-aggregation transition.

Development of Yellow-to-Orange Photoluminescence Molecules Based on Alterations in the Donor Units of Fluorinated Tolanes.

Since the aggregation-induced emission (AIE) phenomenon was first reported by Tang et al., much effort has been devoted to the development of solid-state luminescent molecules by chemists worldwide. Our group successfully developed fluorinated tolanes as novel compact π-conjugated luminophores with blue photoluminescence (PL) in the crystalline state. Moreover, we reported the yellow-green PL molecules based on their electron-density distributions. In the present study, we designed and synthesized fluorinated tolanes with various amine-based donors and evaluated their photophysical properties. The carbazole-substituted fluorinated tolane exhibited strong PL in the solution state, whereas piperidine- or phenothiazine-substituted fluorinated tolanes showed a dramatic decrease in PL efficiency. Notably, fluorinated tolanes with piperidine or phenothiazine substituents displayed yellow-to-orange PL in the crystalline state; this may have occurred because these tolanes exhibited tightly packed structures formed by intermolecular interactions, such as H···F hydrogen bonds, which suppressed the non-radiative deactivation process. Moreover, fluorinated tolanes with amine-based donors exhibited AIE characteristics. We believe that these yellow-to-orange solid PL molecules can contribute to the development of new solid luminescent materials.

Synthesis and Properties of a Water-soluble Fluorescent Probe Based on ICT System for Detection of Ultra-trace SO2 Derivatives.

SO2 and its derivatives are widely present in the environment and living organisms, endangering the environment and human health. Therefore, it is of great significance for the effective detection of sulfur dioxide (SO2) and its hydrated derivatives (HSO3- /SO32-). In this study, based on the mechanism of intramolecular charge transfer (ICT), a water-soluble colorimetric fluorescent probe (E)-2-(4-acetamidostyryl)-3-(5-carboxypentyl)-1, 1-dimethyl-1H-benzo[e]indol-3-ium (ABI) for the detection of SO2 derivatives was successfully synthesized from p-acetaminobenzaldehyde by connecting the benzo[e]indoles cationic fluorophore containing highly activated methyl via C = C double bond, and the ABI structure was characterized by HRMS and 1H NMR, 13 C NMR. Studies have shown that the ABI probe has some advantages such as good selectivity for SO2 derivatives, high sensitivity (detection limit LOD = 14.9 nM), and fast reaction rate. After adding HSO3-, the color of the probe solution changed from light yellow to colorless within 10 s, which provides a simple way to identify bisulfite with the naked eye. Studies on the effect of pH on the fluorescence performance of ABI showed that fluorescence performance of ABI was stable in the range of pH (7.0-10.26). Therefore, ABI is expected to become an effective tool for detecting SO2 derivatives in cells and organisms in the future.

Color-Tunable Indolizine-Based Fluorophores and Fluorescent pH Sensor.

A new fluorescent indolizine-based scaffold was developed using a straightforward synthetic scheme starting from a pyrrole ring. In this fluorescent system, an N,N-dimethylamino group in the aryl ring at the C-3 position of indolizine acted as an electron donor and played a crucial role in inducing a red shift in the emission wavelength based on the ICT process. Moreover, various electron-withdrawing groups, such as acetyl and aldehyde, were introduced at the C-7 position of indolizine, to tune and promote the red shift of the emission wavelength, resulting in a color range from blue to orange (462-580 nm). Furthermore, the ICT effect in indolizine fluorophores allowed the design and development of new fluorescent pH sensors of great potential in the field of fluorescence bioimaging and sensors.

NLOphoric Carbazole-Containing Push-Pull Extended Styryl Chromophores: Study of Photophysical Properties by Solvatochromic and DFT Method.

Carbazole based extended Donor-π-Acceptor styryl dyes with intramolecular charge transfer characteristics were examined for their linear and nonlinear optical properties using solvatochromism, shifts in emission and density functional theory computations. All the extended styryls demonstrated positive solvatochromism. The extended styryl dyes showed largely improved photophysical properties and large Stokes shifts. The donor-acceptor interactions of the extended styryls were investigated by using generalized Mulliken-Hush method. Oscillator strengths and transition state dipole moments have been studied to understand charge transfer within the molecules. The nonlinear optical properties of the extended styryl were investigated by solvatochromic and density functional theory method.

A New Two-Photon Ratiometric Fluorescent Probe for Detecting Alkaline Phosphatase in Living Cells.

Alkaline phosphatase (ALP) is an important diagnostic indicator of many human diseases. To quantitatively track ALP in biosystems, herein, for the first time, we report an efficient two-photon ratiometric fluorescent probe, termed probe 1 and based on classic naphthalene derivatives with a donor-π-acceptor (D-π-A) structure and deprotection of the phosphoric acid moiety by ALP. The presence of ALP causes the cleave of the phosphate group from naphthalene derivatives and the phosphate group changes the ability of the intramolecular charge transfer (ICT) and remarkably alters the probe's photophysical properties, thus an obvious ratiometric signal with an isoemissive point is observed. The fluorescence intensity ratio displayed a linear relationship against the concentration of ALP in the concentration range from 20 to 180 U/L with the limit of detection of 2.3 U/L. Additionally, the probe 1 is further used for fluorescence imaging of ALP in living cells under one-photon excitation (405 nm) or two-photon excitation (720 nm), which showed a high resolution imaging, thus demonstrating its practical application in biological systems.

Highly sensitive fluorescence turn-OFF and reversible chemical sensor for Hg2+ ion based on pyrene appended 2-thiohydantoin.

A novel fluorometric chemical sensor (PY-2TH) based on 2-thiohydantoin (2TH) in conjugation with pyrene (PY) was designed by facile one-pot Knoevenagel condensation reaction and explored for the sensitive and selective detection of Hg2+ ion in solution and solid state methods. Different analytical techniques like NMR and LC-MS concomitantly confirmed the structure of PY-2TH. Absorption and emission studies demonstrate positive solvatochromic effects indicating intramolecular charge transfer in polar solvents. PY-2TH exhibits unprecedented selectivity for detecting Hg2+ ions in tetrahydrofuran (THF) through turn-OFF fluorescence with 90% decrease in the emission intensity with a limit of detection (LOD) of ∼4.4 ppb. The mechanistic investigation through NMR and optical studies confirm the formation of a 2:1 complex between PY-2TH and Hg2+. Thin films of PY-2TH exhibits the J-aggregate formation in the solid state leading to a shift in the emission towards the near-infrared region. Further, we have demonstrated the applicability of PY-2TH for detection of Hg2+ ions and fluorescence imaging in live Zebrafish larvae and the toxicological effects are explored. Cytotoxic evaluation on Zebrafish larval cells revealed that PY-2TH is found to be non-toxic. Detailed analysis demonstrate the potential of PY-2TH for ultra-sensitive Hg2+ ion detection and removal in aqueous environments, highlighting its applicability for identification of metal contamination in live organisms and environmental toxicity.

DFT and TD-DFT Studies of D-π-A Organic Dye Molecules with Different Spacers for highly Efficient Reliable Dye Sensitized Solar Cells.

This study focuses on six D-π-A systems, utilizing diverse π-spacers as bridges. Comprehensive analysis through Density Functional Theory (DFT) and Time-dependent Functional Theory (TD-DFT) methods at B3LYP using 6-31G (d.p) basis set explores geometrical, electrical, optical, photovoltaic, and absorption properties. EHOMO, ELUMO, and energy gap (Egap), for all of these dyes have been determined and discussed using ground state optimization. TD-DFT calculates optical properties, unveiling enhanced excitation energies and HOMO-LUMO energy levels, indicative of improved electron injection and dye regeneration processes. Examination of energy gap, open-circuit voltage (VOC), free energy change (ΔGinject), light harvesting efficiency (LHE), and absorption spectra reveals D4 dye's lower Egap and robust absorption in the visible spectrum. Molecular tailoring emerges as a promising technique for optimizing D-π-A sensitizer design, offering potential advancements in DSSCs applications.

Absorption spectra of p-nitroaniline derivatives: charge transfer effects and the role of substituents.

CONTEXT: Push-pull compounds are model systems and have numerous applications. By changing their substituents, properties are modified and new molecules for different applications can be designed. The work investigates the gas-phase electronic absorption spectra of 15 derivatives of push-pull para-nitroaniline (pNA). This molecule has applications in pharmaceuticals, azo dyes, corrosion inhibitors, and optoelectronics. Both electron-donor and electron-withdrawing groups were investigated. Employing machine learning-derived Hammett's constants σm, σm0, σR, and σI, correlations between substituents and electronic properties were obtained. Overall, the σm0 constants presented the best correlation with HOMO and LUMO energies, whereas the σR constants best agreed with the transition energy of the first band and HOMO-LUMO energy gap. Electron-donors, which have lower σR values, redshift the absorption spectrum and reduce the HOMO-LUMO energy gap. Conversely, electron-withdrawing groups (higher σR's) blueshift the spectrum and increase the energy gap. The second band maximum energies, studied here for the first time, showed no correlation with σ but tended to increase with σ. A comprehensive charge transfer (CT) analysis of the main transition of all systems was also carried out. We found that donors (lower σ's) slightly enhance the CT character of the unsubstituted pNA, whereas acceptors (higher σ's) decrease it, leading to increased local excitations within the aromatic ring. The overall CT variation is not large, except for pNA-SO2H, which considerably decreases the total CT value. We found that the strong electron donors pNA-OH, pNA-OCH3, and pNA-NH2, which have the smallest HOMO-LUMO energy gaps and lowest σ's, have potential for optoelectronic applications. The results show that none of the studied molecules is fluorescent in the gas phase. However, pNA-NH2 and pNA-COOH in cyclohexane and water reveal fluorescence upon solvation. METHODS: We investigated theoretically employing the second-order algebraic diagrammatic construction (ADC(2)) ab initio wave function and time-dependent density functional theory (TDDFT) the gas-phase electronic absorption spectra of 15 derivatives of p-nitroaniline (pNA). The investigated substituents include both electron-donor (C6H5, CCH, CH3, NH2, OCH3, and OH,) and electron-withdrawing (Br, CCl3, CF3, Cl, CN, COOH, F, NO2, and SO2H) substituents.

A mitochondria-targetable fluorescent probe for sulfur dioxide detection and visualisation in living cells.

Sulfur dioxide (SO2) is a one of reactive sulfur species (RSS) that plays significant roles in many physiological processes. While abnormal levels of SO2 in mitochondria have been related to various diseases. Hence, developing suitable fluorescent probe for monitoring SO2 is significant in living organisms. In this research, we designed and synthesized a mitochondrial-target probe Mito-NPH featuring the graft of a strong electron-withdrawing 4-pyridiniumylacrylonitrile unit to an electron-donating naphthalenic unit that intramolecular charge transfer (ICT) process happened. The probe Mito-NPH underwent a nucleophilic addition of HSO3-/SO32-to give fluorescent emission signal change from red to blue and exhibited specific response toward HSO3-/SO32-over other analytes. Moreover, Mito-NPH showed ultrafast response rate (within 10 s) for HSO3-. Importantly, cell imaging results demonstrated that the probe can sense endogenous SO2 in mitochondria.

Fluoranthene-terminated terpyridine ensemble for fluorescence light up and ratiometric chemical sensor for multi toxic metals.

A novel π-electron rich fluoranthene embellished with a phenyl spacer and coupled with terpyridine (TS1) was developed through Diels-Alder reaction. Single crystal X-ray structure evidences the variations in dihedral angles between the fluoranthene and the phenyl unit responsible for development of non-coplanar interactions and stabilized by a wave-like molecular packing in the crystal lattice with weak π-π interaction of 4.125 Å. The peripheral terpyridine of TS1 endows an efficient binding with multiple metal ions by colorimetric and fluorometric methods. TS1 exhibits a ratiometric fluorescence response from sky blue to yellow colour upon the addition of Zn2+ ions with a limit of detection (LOD) of 0.05 ppm. The other metal ions such as Cu2+, Co2+ and Fe2+ demonstrate fluorescence quenching behaviour with LODs of 0.1, 0.3 and 0.7 ppm, respectively. The intramolecular charge transfer (ICT) shows the variation in TS1 emission behaviour upon metal ions interaction and quantitatively discriminates the metal ion concentrations. TS1 conferred a visual colorimetric change from colourless to magenta, enabling naked-eye detection of Fe2+ and showing clear discrimination between Fe2+ and Fe3+ ions for the real-time water samples. Furthermore, we have investigated the effect of TS1 in Zebrafish larvae/embryos and cytotoxicity in human urinary tract transitional cell carcinoma cells (UM-UC-3).

Experimental and Computational studies on Intramolecular charge transfer, Terahertz and Two photon absorption of 3-[(4-Nitrophenyl Azo)]-9H-Carbazole-9-Ethanol (NPACE) from their Vibrational spectra for Optical limiting and NLO applications.

Non-linear optical (NLO) features of 3-[(4-Nitrophenyl Azo)]-9H-Carbazole-9-Ethanol (NPACE) chromophore were investigated by FT-IR, FT-Raman, and UV-visible spectra aided by Density Functional Theory (DFT) using the B3LYP/6-311++G(d,p) basis set of Gaussian 16 W package. It is observed from the DFT calculation that the slight increase in the endocyclic angle of C13 -C14 -C15 and the reduction in exocyclic angle of N40 -N39 -C14 and C15 -C14 -N39 ascertained by experimental XRD values indicating the intramolecular charge-transfer interaction between the carbazole and nitrophenyl group through the diazo bridge. The vibrational contribution to the linear electro-optic effect is 15% of the total hyperpolarizability being calculated at B3LYP/6-311++G (d, p) for the NPACE molecule. It is also observed that the 8a, 19a, and 19b modes of the carbazole ring and the 8a, 8b, and 19b modes of the phenyl ring are found to be simultaneously and intensely active in IR and Raman spectra explaining the charge transfer interactions throughout the molecule. The low value of the HOMO- LUMO energy gap (2.5843 eV) and the deviation between the measured absorption wavelength (3.36 eV) from the computed (3.87 eV), both these facts substantiate the intramolecular charge transfer. The polarizability and first-order hyperpolarizability were calculated as 6.48 × 10-24 and 3.8 × 10-29 esu, respectively. The second harmonic generation (SHG) measurement experiment of NPACE was carried out using the powder method. The SHG efficiency is measured in comparison with the urea standard. The calculated torsional mode at 20 cm-1 is in excellent quantitative agreement with the experimentally determined terahertz absorption peak. The two-photon absorption coefficient of NPACE was estimated to be 0.9 × 10-11 mW-1, which is mainly due to the D-π-A type of molecular structure, and the optical limiting threshold for NPACE was estimated to be 1.52 × 1013 Wm-2 enabling this material as a potential candidate for optical limiting applications.

Bright NIR-Emitting Styryl Pyridinium Dyes with Large Stokes' Shift for Sensing Applications.

Two NIR-emitting donor-π-acceptor (D-π-A) type regioisomeric styryl pyridinium dyes (1a-1b) were synthesized and studied for their photophysical performance and environment sensitivity. The two regioisomers, 1a and 1b, exhibited interesting photophysical properties including, longer wavelength excitation (λex ≈ 530-560 nm), bright near-infrared emission (λem ≈ 690-720 nm), high-fluorescence quantum yields (ϕfl ≈ 0.24-0.72) large Stokes' shift (∆λ ≈ 150-240 nm) and high-environmental sensitivity. Probe's photophysical properties were studied in different environmental conditions such as polarity, viscosity, temperature, and concentration. Probes (1a-1b) exhibited noticeable changes in absorbance, emission and Stokes' shift while responding to the changes in physical environment. Probe 1b exhibited a significant bathochromic shift in optical spectra (∆λ ≈ 20-40 nm) compared to its isomer 1a, due to the regio-effect. Probes (1a-1b) exhibited an excellent ability to visualize bacteria (Bacillus megaterium, Escherichia coli), and yeast (Saccharomyces cerevisiae) via fluorescence microscopy.

Dicyanisophorone-based near-infrared fluorescent probe for the detection of thiophenol and its application in living cells and actual water samples.

This article reports a new type of dicyanisophorone-based near-infrared fluorescent probe for the rapid detection of mercaptophenol by introducing 2,4-dinitrobenzene sulfonate group as a specific recognition group for thiophenol. The probe has a significant large Stokes shift (185 nm). At the same time, it exhibits rapid response, high selectivity and high sensitivity to thiophene. In addition, the fluorescence of the probe at 650 nm has a good linear relationship with the concentration of thiophenol in the range of 0-100 µM, and the detection limit is as low as 65 nM. The probe has been successfully applied to the detection of thiophenol in actual water samples, and has good live cell imaging effects, and at the same time shows the superiority of its low cell toxicity.

Amino-substituted-1,1-dicyano-2,4-diaryl-1,3-butadiene chromophores: Synthesis and photophysical properties.

A series of D-π-A chromophores based on allylidenemalononitrile electron-withdrawing group was designed. The influence of the amino-electron-donating group on the photophysical properties was studied. These compounds, highly thermally stable, exhibit orange-red emission in solution and in solid state. The experimental results have been rationalized by theoretical DFT calculations. The second order nonlinear optical properties were also studied using the electric field induced second harmonic generation (EFISH) method.

Synthesis and Structure-Photophysics Evaluation of 2-N-Amino-quinazolines: Small Molecule Fluorophores for Solution and Solid State.

2-N-aminoquinazolines were prepared by consecutive SN Ar functionalization. X-ray structures display the nitrogen lone pair of the 2-N-morpholino group in conjugation with the electron deficient quinazoline core and thus representing electronic push-pull systems. 2-N-aminoquinazolines show a positive solvatochromism and are fluorescent in solution and in solid state with quantum yields up to 0.73. Increase in electron donor strength of the 2-amino substituent causes a red-shift of the intramolecular charge transfer (ICT) band (300-400 nm); whereas the photoluminescence emission maxima (350-450 nm) is also red-shifted significantly along with an enhancement in photoluminescence efficiency. HOMO-LUMO energies were estimated by a combination of electrochemical and photophysical methods and correlate well to those obtained by computational methods. ICT properties are theoretically attributed to an excitation to Rydberg-MO in SAC-CI method, which can be interpreted as n-π* excitation. 7-Amino-2-N-morpholino-4-methoxyquinazoline responds to acidic conditions with significant increases in photoluminescence intensity revealing a new turn-on/off fluorescence probe.