Effect Of Halogen Research Articles

Computational study of substituent effects on molecular structure, vibrational and electronic properties of fluorene molecule using density functional theory

Density functional theory (DFT) provides a powerful tool for investigating the effects of halogen (F, Cl and Br) substitution on the electronic and structural properties of fluorene. The B3LYP/6-31G (d,p) protocol is a commonly used method in DFT calculations for the optimisation of molecular structures and the calculation of various molecular properties by Gaussian 09 W program. In the case of the fluorene molecule with halogen substitutions, (TD–DFT) calculations can be used to predict its UV–Vis spectrum. The B3LYP density functional model with a 6-31G(d,p) basis set is a common choice for performing (TD–DFT) calculations on molecules. The results showed a decrease in gap energies when electron-withdrawing groups were present in the molecule. A decrease in the gap energy indicates that the molecule is less stable and more reactive.

Halogen Engineering Strategy-Induced Color-Tunable Room Temperature Phosphorescence in Metal-Organic Halides.

Color-tunable room temperature phosphorescence (RTP) materials possess potential applications in multicolor imaging, multichannel anticounterfeiting, and information encryption. Herein, we synthesized two zero-dimensional cadmium-organic halides, (H-aepy)2CdX4 (referred to as CdX-aepy; X = Cl-, Br-; aepy = 3-(2-aminoethyl)pyridine), both of which exhibit long-lived excitation wavelength- and time-dependent RTP. Experimental and theoretical results suggest that the multicolor RTP can be ascribed to the coemission of pristine H-aepy ligands and halogen-affected H-aepys, supporting that suitably introducing halogens can be an efficient strategy for constructing multicolor RTP materials. Additionally, we also demonstrate that the two phosphors can be applied in multichannel anticounterfeiting and information encryption. This work reports two hybrids with color-tunable RTP, as well as provides new insight into the effect of halogens on the regulation of RTP.

Effect of halogens on 3-[4-(dimethylamino) phenyl]-1-phenylprop-2-en-1-ones: development of a new class of monoamine oxidase-B inhibitors

Five dimethylamino-based chalcone derivatives (AC) were synthesized and evaluated for their inhibition degree against monoamine oxidase (MAO) enzymes. All AC compounds showed better inhibitory activity against MAO-B than that against MAO-A. AC4 showed the highest inhibitory ability with an IC50 value of 0.020 µM, similar to that of a reference drug safinamide (IC50 = 0.019 µM) against MAO-B, followed by AC1 (IC50 = 0.068 µM) and AC3 (IC50 = 0.083 µM). Substituent -F in ring A (AC4) increased the MAO-B inhibition, followed by -H (AC1), -Br (AC3), and -Cl (AC2). The selectivity index (SI) value of AC4 was high (SI = 82.00) as well as other compounds (44.41 to 98.15). AC4 was found to be a reversible inhibitor as confirmed through analysis using the dialysis method. Interestingly, AC4 was observed to be a noncompetitive MAO-B inhibitor with a rare case and with Ki values of 0.011 ± 0.0036 µM. These experiments confirmed that AC4 is a reversible and potent selective inhibitor of MAO-B. Molecular docking experiments revealed that AC4 showed the highest inhibitory activity with a docking score (-9.510 kcal/mol). A study using molecular dynamics modeling revealed that the protein–ligand complex was more stable. It was observed that AC4 was non-cytotoxic in the study using L929 cell line. In conclusion, compound AC4 shows promise as a MAO-B inhibitor.

Halogen Impact on the Supramolecular Organization of Chiral Phthalimide EmittersDisplaying Room Temperature Phosphorescence.

Room temperature phosphorescence from organic materials has attracted an increasing attention in the recent years due to their potential application in various advancing technologies, notably in bioimaging and displays. In this context, heavy atoms such as halogen ones revealed useful tools to enhance the spin-orbit coupling (SOC) of molecular organic phosphors. However, the effect of halogen at the supramolecular level remains less understood, especially in the field of molecular crystals where additional factors can impact the phosphorescence emission. Here, we investigate external effect of halogens on the phosphorescence of chiral phthalimides molecular crystals. The results show that changing the nature of the halogen atom onto the phthalimide core leads to an evolution of the photophysical properties of the materials which does not necessarily follow the classical trend imposed by the expected internal heavy atom effect. Beyond this aspect, we showed that the halogen atom has a profound impact on the packing between the chromophores at the supramolecular level which is of paramount importance towards the optical properties (PLQY and lifetimes) of the different phosphors examined.

Effects of halogens and alkali metals on guanidinium-ethylammonium hybrid-doped perovskite photovoltaic devices

Effects of substitution of halogen anions and addition of alkali metal cations for guanidinium (GA)-ethylammonium (EA) hybrid-doped perovskite solar cells were investigated by fabricating devices and comparing their photovoltaic properties. The halogen compositions of the additives were found to contribute to the improvement of preferred orientations of perovskite crystals, and the order of the effectiveness was I, Cl, and Br. In addition, the addition of alkali metal cations contributed to improvement of the conversion efficiencies, and 3 % addition of cesium at the CH3NH3 site was the most effective. It was also found that the short-circuit current densities and fill factors depended on the (100) preferred crystal orientation of the perovskite compounds.

The Halogenation Effect Induces a Variety of Switchable Phase Transition and Second-Harmonic-Generation Materials.

Halogen engineering offers a means of enhancing the physical properties of materials by fine-tuning the rotational energy barrier and dipole moment, which proved to be effective in achieving switchable phase transitions and optical responses in materials. In this work, by substituting the methyl group in ligand N-ethyl-1,5-diazabicyclo[3.3.0]octane (CH3CH2-3.3.0-Dabco) with halogen atoms X (Cl or Br) and then contining to react it with FeBr3 in a HBr aqueous solution, we successfully synthesized three kinds of organic-inorganic hybrid switchable phase-change materials, [CH3CH2-3.3.0-Dabco]FeBr4 (1), [ClCH2-3.3.0-Dabco]FeBr4 (2), and [BrCH2-3.3.0-Dabco]FeBr4 (3), which were fully characterized by single-crystal X-ray diffraction and variable-temperature powder X-ray diffraction. Compared to compound 1, compounds 2 and 3 show two pairs of reversible phase transitions, dielectric anomalies, and a second-harmonic-generation effect, which are successfully induced due to the halogen substitution. This study offers an effective molecular design strategy for the exploration and construction of iron halide organic-inorganic hybrid materials with temperature-adjustable physical properties.

Effect of Halogenation on the Photocatalytic Hydrogen Evolution Performance of Tetrazine Polymers

Effect of Halogenation on the Photocatalytic Hydrogen Evolution Performance of Tetrazine Polymers

Substituent effects of halogens on the excited-state intermolecular proton transfer reactions.

Fluorescent aromatic urea compounds undergo excited-state intermolecular proton transfer (ESPT) in the presence of acetate anions to produce an excited state of the tautomer (T*) from the excited state of the complex (N*), resulting in dual fluorescence. Herein, we performed spectroscopic measurements of anthracen-1-yl-3-phenylurea derivatives with substituents, -CF3, -F, or -Cl, at the p-position of the phenyl group in the presence of acetate to investigate the substituent effects on the ESPT reaction and the deactivation processes of N* and T*. Kinetic analysis showed that the reverse ESPT rate constant (k-PT) depended on the respective substituents, suggesting that each substituent may influence the reverse ESPT process differently. In particular, since the electron-withdrawing properties of -F are estimated by the - I and + Iπ effects, it is plausible that -F has a slight electron-donating property and influences the reverse process from T* to N* in the excited state. This study shows that it is possible to control emission by selecting specific substituents in the ESPT system.

Halogenated Dibenzo[f,h]quinoxaline Units Constructed 2D-Conjugated Guest Acceptors for 19% Efficiency Organic Solar Cells.

Halogenation of Y-series small-molecule acceptors (Y-SMAs) is identified as an effective strategy to optimize photoelectric properties for achieving improved power-conversion-efficiencies (PCEs) in binary organic solar cells (OSCs). However, the effect of different halogenation in the 2D-structured large π-fused core of guest Y-SMAs on ternary OSCs has not yet been systematically studied. Herein, four 2D-conjugated Y-SMAs (X-QTP-4F, including halogen-free H-QTP-4F, chlorinated Cl-QTP-4F, brominated Br-QTP-4F, and iodinated I-QTP-4F) by attaching different halogens into 2D-conjugation extended dibenzo[f,h]quinoxaline core are developed. Among these X-QTP-4F, Cl-QTP-4F has a higher absorption coefficient, optimized molecular crystallinity and packing, suitable cascade energy levels, and complementary absorption with PM6:L8-BO host. Moreover, among ternary PM6:L8-BO:X-QTP-4F blends, PM6:L8-BO:Cl-QTP-4F obtains a more uniform and size-suitable fibrillary network morphology, improved molecular crystallinity and packing, as well as optimized vertical phase distribution, thus boosting charge generation, transport, extraction, and suppressing energy loss of OSCs. Consequently, the PM6:L8-BO:Cl-QTP-4F-based OSCs achieve a 19.0% efficiency, which is among the state-of-the-art OSCs based on 2D-conjugated Y-SMAs and superior to these devices based on PM6:L8-BO host (17.70%) and with guests of H-QTP-4F (18.23%), Br-QTP-4F (18.39%), and I-QTP-4F (17.62%). The work indicates that halogenation in 2D-structured dibenzo[f,h]quinoxaline core of Y-SMAs guests is a promising strategy to gain efficient ternary OSCs.

The Effects of Halogen (Cl, Br) Decorating on the Gas Adsorption Behaviors of the Pristine Black Phosphorene: A First-Principles Study

As a novel two-dimensional (2D) material, black phosphorene (BP) finds wide applications in gas adsorption and detection devices due to its distinctive optical, thermoelectric, and surface properties. However, numerous studies have demonstrated that BP exhibits strong selectivity towards gas adsorption and displays significant affinity towards gas molecules containing the element N, thereby greatly impeding its utilization in gas detection. To partially compensate for this deficiency, this study investigates the impact of halogen atom decoration on the adsorption behavior of BP towards CO2, H2O, and O2 molecules. Furthermore, a comparison is made between the variations in gas adsorption energy with and without decorated halogen atoms. The results showed that the adsorbates of CO2, H2O, and O2 molecules and halogen atoms (Cl, Br) adsorbed at the top (T) site of BP was much stronger than those at the bridge (B) and the hollow (H) sites of the P-P bond of BP, owing to their low adsorption energies. After the t position of BP is modified by the halogen (Cl, Br) atom, the optimal adsorption of CO2 changes from −0.85 eV to −1.70 eV (Cl) and −1.64 eV (Br), and the optimal adsorption of H2O changes from −0.72 eV to −1.48 eV (Cl) and −1.23 eV (Br), respectively. The adsorption properties were significantly enhanced. That is to say, the gas adsorption properties of BP have been largely improved by halogen Cl (Br) atoms decorating.

Influence of Solvents and Halogenation on ESIPT of Benzimidazole Derivatives for Designing Turn-on Fluorescence Probes.

This work reports a theoretical investigation of the solvent polarity as well as the halogenation of benzimidazole derivatives during excited state intramolecular proton transfer (ESIPT). It details how the environment and halogen substitution may contribute to the efficiency of ESIPT upon keto-enol tautomerism and exploits this effect to design fluorescence sensing. For this purpose, we first examine the conformational equilibrium of benzimidazole derivatives containing different halogen atoms, which results in intramolecular proton transfer, using density-functional theory (DFT) combined with the polarizable continuum model (PCM). Then we evaluate the fluorescence of the benzimidazole derivatives in different dielectric constants within time-dependent DFT (TD-DFT) approaches. Our results quantitatively allow the determination of large Stokes shifts in nonpolar solvents around 100 nm. These theoretical results are in agreement with experimental solvatochromism studies of benzimidazoles. The effect of halogenation, with fluorine, chlorine, and bromine, is less important than solvent polarization when ESIPT takes place. Thus, halogenation can be properly chosen depending on the interest of the synthesis of benzimidazole-based turn-on fluorescence in appropriate solvents.

Effect of boron halogenation on dihydrogen bonds: A quantum mechanical approach

Effect of boron halogenation on dihydrogen bonds: A quantum mechanical approach

Modulating 3d Charge State via Halogen Ions in Neighboring Molecules of Metal-Organic Frameworks for Improving Water Oxidation.

Modulating the coordination environment of the metal active center is an effective method to boost the catalytic performances of metal-organic frameworks (MOFs) for oxygen evolution reaction (OER). However, little attention has been paid to the halogen effects on the ligands engineering. Herein, a series of MOFs X─FeNi-MOFs (X = Br, Cl, and F) is constructed with different coordination microenvironments to optimize OER activity. Theoretical calculations reveal that with the increase in electronegativity of halogen ions in terephthalic acid molecular (TPA), the Bader charge of Ni atoms gets larger and the Ni-3d band center and O-2p bands move closer to the Fermi level. This indicates that an increase in ligand negativity of halogen ions in TPA can promote the adsorption ability of catalytic sites to oxygen-containing intermediates and reduce the activation barrier for OER. Experimental also demonstrates that F─FeNi-MOFs exhibit the highest catalytic activity with an ultralow overpotential of 218mV at 10mAcm-2, outperforming most otate-of-the-art Fe/Co/Ni-based MOFs catalysts, and the enhanced mass activity by seven times compared with that for the sample before ligands engineering. This work opens a new avenue for the realization of the modulation of NiFe─O bonding by halogen ion in TPA and improves the OER performance of MOFs.

A Halogen‐Bond‐Driven Artificial Chloride‐Selective Channel Constructed from 5‐Iodoisophthalamide‐based Molecules

AbstractDespite considerable emphasis on advancing artificial ion channels, progress is constrained by the limited availability of small molecules with the necessary attributes of self‐assembly and ion selectivity. In this study, a library of small molecules based on 5‐haloisophthalamide and a non‐halogenated isophthalamide were examined for their ion transport properties across the lipid bilayer membranes, and the finding demonstrates that the di‐hexyl‐substituted 5‐iodoisophthalamide derivative exhibits the highest level of activity. Furthermore, it was established that the highest active compound facilitates the selective chloride transport that occurs via an antiport‐mediated mechanism. The crystal structure of the compound unveils a distinctive self‐assembly of molecules, forming a zig‐zag channel pore that is well‐suited for the permeation of anions. Planar bilayer conductance measurements proved the formation of chloride selective channels. A molecular dynamics simulation study, relying on the self‐assembled component derived from the crystal structure, affirmed the paramount significance of intermolecular hydrogen bonding in the formation of supramolecular barrel‐rosette structures that span the bilayer. Furthermore, it was demonstrated that the transport of chloride across the lipid bilayer membrane is facilitated by the synergistic effects of halogen bonding and hydrogen bonding within the channel.

A Halogen-Bond-Driven Artificial Chloride-Selective Channel Constructed from 5-Iodoisophthalamide-based Molecules.

Despite considerable emphasis on advancing artificial ion channels, progress is constrained by the limited availability of small molecules with the necessary attributes of self-assembly and ion selectivity. In this study, a library of small molecules based on 5-haloisophthalamide and a non-halogenated isophthalamide were examined for their ion transport properties across the lipid bilayer membranes, and the finding demonstrates that the di-hexyl-substituted 5-iodoisophthalamide derivative exhibits the highest level of activity. Furthermore, it was established that the highest active compound facilitates the selective chloride transport that occurs via an antiport-mediated mechanism. The crystal structure of the compound unveils a distinctive self-assembly of molecules, forming a zig-zag channel pore that is well-suited for the permeation of anions. Planar bilayer conductance measurements proved the formation of chloride selective channels. A molecular dynamics simulation study, relying on the self-assembled component derived from the crystal structure, affirmed the paramount significance of intermolecular hydrogen bonding in the formation of supramolecular barrel-rosette structures that span the bilayer. Furthermore, it was demonstrated that the transport of chloride across the lipid bilayer membrane is facilitated by the synergistic effects of halogen bonding and hydrogen bonding within the channel.

Halogen-modulated mechanical force-induced luminescence enhancement and chromism of AIE-active tetraphenylethylene-based chalcone derivatives

In this paper, four new tetraphenylethylene-based chalcone derivatives (E)-1-phenyl-3-(4-(1,2,2-triphenylvinyl)phenyl)prop-2-en-1-one (PLPE), (E)-1-(4-fluorophenyl)-3-(4-(1,2,2-triphenylvinyl)phenyl)prop-2-en-1-one (PLPE-F),(E)-1-(4-chlorophenyl)-3-(4-(1,2,2-triphenylvinyl)phenyl)prop-2-en-1-one (PLPE-Cl), (E)-1-(4-bromophenyl)-3-(4-(1,2,2-triphenylvinyl)phenyl)prop-2-en-1-one (PLPE-Br) with different halogen substitutions were reported, and the effects of halogens on their photophysical properties, aggregation-induced emission behaviors and mechano-responsive luminescent properties were systematically investigated. Interestingly, aggregation-induced emission enhancement (AIEE) behaviors were observed for PLPE, PLPE-F, PLPE-Cl, and PLPE-Br. Moreover, upon grinding, all of the four compounds displayed mechanical force-induced luminescence enhancement and red-shifted behaviors, which was found to be reversible in the case of fuming with dichloromethane (DCM) vapors or heat treatment. In particular, upon grinding, PLPE-F showed the highest contrast fluorescence response behaviors (red-shifted 49 nm and solid fluorescence quantum yield increased 20-fold). Furthermore, the results of powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC) and field emission scanning electron microscopy (FESEM) measurements indicated that reversible phase transitions between the ordered crystalline state and the disordered amorphous form was crucial to their interesting mechanical force-induced luminescence enhancement and chromism. And the obvious red shifts of fluorescence emission are ascribed to the increased molecular conjugations via the planarization of molecular conformations. Moreover, halogen-substituted PLPE-F, PLPE-Cl, PLPE-Br have more twisted conformations than PLPE, which are responsible for their higher contrast mechanical force-induced luminescence chromism. Hence, the present study provides a new strategy to construct new advanced high-contrast mechanical force-induced luminescence enhancement and chromism luminescent materials with the introduction of halogen atoms.

Abstract 4165: Influence of halogens in squaraine dye on optoacoustic signal

Abstract Optoacoustic imaging has grown in clinical relevance due to inherent advantages in sensitivity, resolution, and contrast, compared to standard modalities, such as fluorescence. However, guiding principles for development of small molecule contrast agents specific for optoacoustic imaging is lacking. This study assesses the influence of specific structural features of small molecule dyes, specifically squaraine dyes, that result in optoacoustic activity. Through computational models, in vitro testing, and in vivo experimentation this study assesses the effects of halogens on small molecule squaraine dyes to increase optoacoustic signal. By using the aid of our computational model, we decorated the squaraine scaffold with heavy halogenation of squaraines increased optoacoustic activity (2.12 a.u. vs. 0.21 a.u., p<0.001). Density functional theory models suggest the origin of increased optoacoustic signal is due to increases in transition dipole moment which manifested experimentally as increased absorbance in the NIR wavelength range and decreased fluorescence quantum yield, respectively. This study provides an insight into the structure-function relationships that lead to guiding principles for designing optoacoustic-specific contrast agents. Further developments of squaraines and other types of optoacoustic agents will further increase relevance of optoacoustic imaging in a clinical setting. Citation Format: Kavita Belligund, William MacCuaig, Carly Wickizer, Yihan Shao, Lacey R. McNally. Influence of halogens in squaraine dye on optoacoustic signal [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2024; Part 1 (Regular Abstracts); 2024 Apr 5-10; San Diego, CA. Philadelphia (PA): AACR; Cancer Res 2024;84(6_Suppl):Abstract nr 4165.

Investigating the effect of mixed halogens in the properties of copper cysteamine by density functional theory

A new type of copper cysteamine photosensitizer, Cu-Cy: Cu3Cl (SR)2 (R = CH2CH2NH2), was reported and later, there was another experimental report of Cu-Cy synthesis with other halogen elements (Cu-Cy-X, X = F, Br, and I), these later group of cysteamines contained Cl as an impurity. To realize the full potential applications of these cysteamines as photosensitizers, it is imperative to fundamentally understand the effect of Cl on the stability and optical properties of Cu-Cy-F/Br/I. In this paper, the stability of Cl-doped Cu-Cy-X (X = F, Br, and I) and their electronic and optical properties pertaining to their application as photosensitizers were investigated by using density functional theory (DFT). It was found that mixing Cu-Cy-Br and Cu-Cy-I with Cl increased their thermodynamic stability as well as made the materials mechanically harder. In addition, mixing halogens in Cu-Cy rendered a significant impact on their optical properties, namely the mixing affected Cu-Cy's deexcitation to their ground states during the photosensitizing process. In addition, it was found that after the initial photoexcitation within these Cu-cysteamines, the intersystem crossing can take place due to spin–orbit coupling from the Cu atoms.

Adsorption and reversible detection of toxic halogens gases at room temperature by two-dimensional Al2SSe for occupational sustainability

Current treatment for inhalational halogens poisoning involves providing supportive care, which includes administering humidified oxygen and managing the airway. Since toxic effects of halogens cannot be reversed, sensors with high sensitivity and good reversibility for detecting the relatively lower concentration yet noxious halogens becomes particularly significant and enticing. Herein, the structural and optoelectronic properties of toxic F2 and Cl2 gas molecules adsorbed on highly stable Al2SSe monolayer have been systematically studied by means of first-principles calculations based on density functional theory (DFT). Favorable adsorption sites of said molecules on Al2SSe were carefully examined. The relatively high, negative adsorption energy for F2 and Cl2 indicate that the adsorption process is exothermic and the molecules could be stably adsorbed on Al2SSe monolayer. This characteristic, combined with the substantial charge transfer (0.15–0.55 |e|), drastic change in work function, complete reversibility due to recovery time in 10−1 s scale and distinct optical response, render Al2SSe monolayer a viable option for utilization as either surface work functions transistor or optical chemical resistor for detecting these gases. Pearson correlation coefficient (PCC) analysis of theoretical recovery time and response value indicates that band gap change and electron transfer are the primary influencing factors. Selectivity analysis reveals that common compound forms of halogens and atmospheric molecules such as HF, HCl, N2, O2, H2 and H2O are either physically adsorbed or inert with extremely low adsorption energies on Al2SSe, prompting high F2 and Cl2 selectivity. These outcomes acclaim the exciting prospects of developing Al2SSe monolayer for specific, occupational related ultrahigh-sensitivity F2 and Cl2 sensing nanodevices.

Palladium(II)‐Imidoyl Complexes: A New Piece in the Puzzle of Organopalladium Anticancer Agents

AbstractOur search of new organopalladium compounds able to promote an effective antiproliferative action towards ovarian cancer cells continues. In this paper we have examined for the first time the anticancer activity of palladium imidoyl complexes, for which two different types of phosphines have been chosen as ancillary ligands: i) PTA and DAPTA to take advantage from their solubility in aqueous environment, and ii) dppf for combining the action of the Pd‐imidoyl fragment with that, well‐known, of ferrocene. The synthetic protocols as well as the exhaustive characterisation of the complexes through spectroscopic and diffractometric methods are described. In vitro tests carried out to assess the cytotoxicity of the new compounds towards two ovarian cancer cell lines (one cisplatin sensitive and the other cisplatin resistant) have revealed an interesting effect of the halide coordinated to the palladium centre (halogen effect). Moreover, all complexes have shown the same activity against the cisplatin‐sensitive (A2780) and cisplatin‐resistant (A2780cis) cell lines, suggesting a different mode of action with respect to the “classical” platinum‐based drugs. Finally, a selection of the most active compounds has shown an interesting selectivity towards ovarian cancer cells.