Ortho-substituted Research Articles

Electrochemistry of Innocent Cyanocobalt Corroles

The electrochemical and spectroscopic properties of numerous transition metal corroles have been examined under a wide variety of solution conditions with particular interest being placed on the innocent or non-innocent nature of the corrole macrocycle and oxidation state of the central metal ion. The innocence of the redox active corrole ligand, as well as the half-wave potentials and sites of electron transfer are known to be strongly influenced by the type of central metal ion, degree of axial coordination (i.e. four-, five- or six-coordinate) and type of peripheral substituents at the meso or β-pyrrole positions of the corrole ligand. Our laboratories have previously investigated five- and six-coordinate cobalt corroles with P, N or O donor ligands and a wide variety of peripheral corrole substituents. In this work, we describe the intriguing electrochemical and spectroscopic properties of several innocent cobalt(III) corroles which are axially ligated by two pyridine molecules, one or two cyanide ions or one pyridine and one cyanide ion. Examples of the investigated corroles are shown in Chart 1 and represented as [(R)3CorCo(Py)2], [(R)3CorCo(Py)(CN)]-, [(R)3CorCo(CN)]- and [(R)3CorCo(CN)2]2- where (R)3Cor is the corrole macrocycle and R is one of several meso-substituents. Figure 1

Quantitative Structure-Property Relationship Modelling for the Prediction of Singlet Oxygen Generation by Heavy-Atom-Free BODIPY Photosensitizers*.

Heavy‐atom‐free sensitizers forming long‐living triplet excited states via the spin‐orbit charge transfer intersystem crossing (SOCT‐ISC) process have recently attracted attention due to their potential to replace costly transition metal complexes in photonic applications. The efficiency of SOCT‐ISC in BODIPY donor‐acceptor dyads, so far the most thoroughly investigated class of such sensitizers, can be finely tuned by structural modification. However, predicting the triplet state yields and reactive oxygen species (ROS) generation quantum yields for such compounds in a particular solvent is still very challenging due to a lack of established quantitative structure‐property relationship (QSPR) models. In this work, the available data on singlet oxygen generation quantum yields (ΦΔ) for a dataset containing >70 heavy‐atom‐free BODIPY in three different solvents (toluene, acetonitrile, and tetrahydrofuran) were analyzed. In order to build reliable QSPR model, a series of new BODIPYs were synthesized that bear different electron donating aryl groups in the meso position, their optical and structural properties were studied along with the solvent dependence of singlet oxygen generation, which confirmed the formation of triplet states via the SOCT‐ISC mechanism. For the combined dataset of BODIPY structures, a total of more than 5000 quantum‐chemical descriptors was calculated including quantum‐chemical descriptors using density functional theory (DFT), namely M06‐2X functional. QSPR models predicting ΦΔ values were developed using multiple linear regression (MLR), which perform significantly better than other machine learning methods and show sufficient statistical parameters (R=0.88–0.91 and q2=0.62–0.69) for all three solvents. A small root mean squared error of 8.2 % was obtained for ΦΔ values predicted using MLR model in toluene. As a result, we proved that QSPR and machine learning techniques can be useful for predicting ΦΔ values in different media and virtual screening of new heavy‐atom‐free BODIPYs with improved photosensitizing ability.

Bis(2-nitrophenyl) selenide, bis(2-aminophenyl) selenide and bis(2-aminophenyl) telluride: structural and theoretical analysis.

Three organoselenium and organotellurium compounds containing ortho substitutents, namely, bis(2-nitrophenyl) selenide, C12H8N2O4Se, 2, bis(2-aminophenyl) selenide, C12H12N2Se, 3, and bis(2-aminophenyl) telluride, C12H12N2Te, 7, have been investigated by both structural and theoretical methods. In the structures of all three compounds, there are intramolecular contacts between both Se and Te with the ortho substituents. In the case of 2, this is achieved by rotation of the nitro group from the arene plane. For 3, both amino groups exhibit pyramidal geometry and are involved in intramolecular N-H...Se interactions, with one also participating in intermolecular N-H...N hydrogen bonding. While 3 and 7 are structurally similar, there are some significant differences. In addition to both intramolecular N-H...Te interactions and intermolecular N-H...N hydrogen bonding, 7 also exhibits intramolecular N-H...N hydrogen bonding. In the packing of these molecules, for 2, there are weak intermolecular C-H...O contacts and these, along with the O...N interactions mentioned above, link the molecules into a three-dimensional array. For 3, in addition to the N-H...N and N-H...Se interactions, there are also weak intermolecular C-H...Se interactions, which also link the molecules into a three-dimensional array. On the other hand, 7 shows intermolecular N-H...N interactions linking the molecules into R22(16) centrosymmetric dimers. In the theoretical studies, for compound 2, AIM (atoms in molecules) analysis revealed critical points in the Se...O interactions with values of 0.017 and 0.026 a.u. These values are suggestive of weak interactions present between Se and O atoms. For 3 and 7, the molecular structures displayed intramolecular, as well as intermolecular, hydrogen-bond interactions of the N-H...N type. The strength of this hydrogen-bond interaction was calculated by AIM analysis. Here, the intermolecular (N-H...N) hydrogen bond is stronger than the intramolecular hydrogen bond. This was confirmed by the electron densities for 3 and 7 [ρ(r)= 0.015 and 0.011, respectively].

ZW800-PEG: A Renal Clearable Zwitterionic Near-Infrared Fluorophore for Potential Clinical Translation.

Near-infrared (NIR) fluorescence imaging has advanced medical imaging and image-guided interventions during the past three decades. Despite tremendous advances in imaging devices, surprisingly only a few dyes are currently available in the clinic. Previous fluorophores, ZW800-1A and ZW800-1C, significantly improved the poor performance of the FDA-approved indocyanine green. However, ZW800-1A is not stable in serum and ZW800-1C induces severe stacking in aqueous media. To solve such dilemmas, ZW800-PEG was designed by introducing a flexible yet stable thiol PEG linker. ZW800-PEG shows high solubility in both aqueous and organic solvents, thus improving renal clearance with minimal binding to serum proteins during systemic circulation. The sulfide group on the meso position of the heptamethine core improves serum stability and physicochemical properties including the maximum emission wavelength shift to 800 nm, enabling the use of ZW800-PEG for image-guided interventions and augmenting photothermal therapy.

ZW800‐PEG: A Renal Clearable Zwitterionic Near‐Infrared Fluorophore for Potential Clinical Translation

AbstractNear‐infrared (NIR) fluorescence imaging has advanced medical imaging and image‐guided interventions during the past three decades. Despite tremendous advances in imaging devices, surprisingly only a few dyes are currently available in the clinic. Previous fluorophores, ZW800‐1A and ZW800‐1C, significantly improved the poor performance of the FDA‐approved indocyanine green. However, ZW800‐1A is not stable in serum and ZW800‐1C induces severe stacking in aqueous media. To solve such dilemmas, ZW800‐PEG was designed by introducing a flexible yet stable thiol PEG linker. ZW800‐PEG shows high solubility in both aqueous and organic solvents, thus improving renal clearance with minimal binding to serum proteins during systemic circulation. The sulfide group on the meso position of the heptamethine core improves serum stability and physicochemical properties including the maximum emission wavelength shift to 800 nm, enabling the use of ZW800‐PEG for image‐guided interventions and augmenting photothermal therapy.

Novel meso-substituted porphyrin derivatives and its potential use in photodynamic therapy of cancer

BackgroundPhotodynamic therapy (PDT) is an anticancer treatment that utilizes the interaction of light and a photosensitiser (PS), promoting tumour cell death mediated by generation of reactive oxygen species. In this study, we evaluated the in vitro photoactivity of four meso-substituted porphyrins and a porphyrin coupled to a fullerene.MethodsThe cell line employed was the LM3 mammary adenocarcinoma, and the PS with the best photokilling activity was administered to mice bearing the LM3 subcutaneously implanted adenocarcinoma. The TEMCP4+ porphyrin and its analogue TEMCC4+ chlorine contain four identical carbazoyl substituents at the meso positions of the tetrapyrrolic macrocycle and have A4 symmetry. The TAPP derivative also has A4 symmetry, and it is substituted at the meso positions by aminopropoxy groups. The DAPP molecule has ABAB symmetry with aminopropoxy and the trifluoromethyl substituents in trans positions. The TCP-C604+ dyad is formed by a porphyrin unit covalently attached to the fullerene C60.ResultsThe PSs are taken up by the cells with the following efficiency: TAPP> TEMCP4+ = TEMCC4+ > DAPP >TCP-C604+, and the amount of intracellular PS correlates fairly with the photodamage degree, but also the quantum yields of singlet oxygen influence the PDT outcome. TAPP, DAPP, TEMCC4+ and TEMCP4+ exhibit high photoactivity against LM3 mammary carcinoma cells, being TAPP the most active. After topical application of TAPP on the skin of mice bearing LM3 tumours, the molecule is localized mainly in the stratum corneum, and at a lower extent in hair follicles and sebaceous glands. Systemic administration of TAPP produces a tumour: normal skin ratio of 31.4, and high accumulation in intestine and lung.ConclusionThe results suggest a potential use of topical TAPP for the treatment of actinic keratosis and skin adnexal neoplasms. In addition, selectivity for tumour tissue after systemic administration highlights the selectivity of and potentiality of TAPP as a new PS.

Low-melting phthalonitrile monomers containing maleimide group: Synthesis, dual-curing behavior, thermal and mechanical properties

Novel dual-functional phthalonitrile monomers containing a maleimide group were synthesized and characterized. Ortho, meta, and para isomers were obtained and only the meta-isomer can be considered as a low melting phthalonitrile monomer with a melting point of 107.4°С. Analysis of the dual-curing behavior of monomers showed radical homopolymerization of maleimides followed by phthalonitrile polymerization with the formation of isoindoline, triazine, and phthalocyanine ring structures. Two alternative copolymerization processes of maleimide groups via ene reaction and ring-opening amidation were investigated. The approach of dual-curing maleimide and phthalonitrile fragments in a single molecule allowed combining the excellent inherent mechanical properties of bismaleimide resins and the outstanding thermo-oxidative stability of phthalonitriles. After curing of both functional groups impact strength was as high as 11.81 kJ m−2, flexural strength was 108 MPa, Young's modulus was 4.38 GPa. On the contrary, Tg of this polymeric system was above 370°С and T5% was higher than 450°С in air.

(Trifluoromethoxy)Phenylboronic Acids: Structures, Properties, and Antibacterial Activity

Three isomers of (trifluoromethoxy)phenylboronic acids were studied in the context of their physicochemical, structural, antimicrobial and spectroscopic properties. They were characterized by 1H, 13C, 11B and 19F NMR spectroscopy. The acidity of all the isomers was evaluated by both spectrophotometric and potentiometric titrations. The introduction of the -OCF3 group influences the acidity, depending, however, on the position of a substituent, with the ortho isomer being the least acidic. Molecular and crystal structures of ortho and para isomers were determined by the single crystal XRD method. Hydrogen bonded dimers are the basic structural motives of the investigated molecules in the solid state. In the case of the ortho isomer, intramolecular hydrogen bond with the -OCF3 group is additionally formed, weaker, however, than that in the analogous -OCH3 derivative, which has been determined by both X-Ray measurements as well as theoretical DFT calculations. Docking studies showed possible interactions of the investigated compounds with LeuRS of Escherichia coli. Finally, the antibacterial potency of studied boronic acids in vitro were evaluated against Escherichia coli and Bacillus cereus.

The TW Hya Rosetta Stone Project IV: A Hydrocarbon-rich Disk Atmosphere

Abstract Connecting the composition of planet-forming disks with that of gas giant exoplanet atmospheres, in particular through C/O ratios, is one of the key goals of disk chemistry. Small hydrocarbons like C2H and C3H2 have been identified as tracers of C/O, as they form abundantly under high C/O conditions. We present resolved c–C3H2 observations from the TW Hya Rosetta Stone Project, a program designed to map the chemistry of common molecules at 15–20 au resolution in the TW Hya disk. Augmented by archival data, these observations comprise the most extensive multi-line set for disks of both ortho and para spin isomers spanning a wide range of energies, E u = 29–97 K. We find the ortho-to-para ratio of c–C3H2 is consistent with 3 throughout extent of the emission, and the total abundance of both c–C3H2 isomers is (7.5–10) × 10−11 per H atom, or 1%–10% of the previously published C2H abundance in the same source. We find c–C3H2 comes from a layer near the surface that extends no deeper than z/r = 0.25. Our observations are consistent with substantial radial variation in gas-phase C/O in TW Hya, with a sharp increase outside ∼30 au. Even if we are not directly tracing the midplane, if planets accrete from the surface via, e.g., meridional flows, then such a change should be imprinted on forming planets. Perhaps interestingly, the HR 8799 planetary system also shows an increasing gradient in its giant planets’ atmospheric C/O ratios. While these stars are quite different, hydrocarbon rings in disks are common, and therefore our results are consistent with the young planets of HR 8799 still bearing the imprint of their parent disk’s volatile chemistry.

Aromaticity of ortho and meta 8-Cycloparaphenylene and Their Dications: Induced Magnetic Field Analysis with Localized and Delocalized Orbitals in Strained Nanohoops.

Dications of cycloparaphenyles ([n]CPPs) are known to exhibit in-plane global aromaticity, contained in a nanobelt structure. Recently synthesized ortho and meta isomers of [n]CPPs break the radial symmetry of π structure incorporating perpendicular oriented π orbitals. Herein we set to explore the aromaticity of neutral and dicationic ortho and meta isomers of [8]CPP by dissecting the induced magnetic field to contributions of the twofold radial/perpendicular π system using delocalized canonical molecular orbitals (CMO), and introducing the natural localized molecular orbitals (NLMO) analysis with DFT methods. The dications sustain a reduced global aromatic character of the radial π system under a perpendicular orientation of the external field which declines from ortho to meta isomer and reinforces local aromaticity of ortho ring while it destroys aromaticity of meta ring. Aromaticity variations are determined by symmetry governed rotational excitations of frontier π orbitals. The parallel orientation reveals a substantial reduction of local aromaticity verified with NICSπ analysis and electron delocalization indices.

Visual recognition of ortho-xylene based on its host-guest crystalline self-assembly with α-cyclodextrin

HypothesisDistinguishing substituted aromatic isomers is a challenging task because of the great similarity of their physicochemical properties. Considering xylene isomers have drastically different geometrical shapes, we predict this would show great impact on the self-assembling behavior of various xylene isomer@cyclodextrin inclusion complex. ExperimentsThrough host–guest crystalline self-assembly, among three isomers, only ortho-xylene is capable to form hydrogels with α-cyclodextrin. ROESY NMR, molecular simulations and circular dichroism spectra suggest that the ortho selectivity comes from the difference in the conformation of host–guest building block. The larger volume, and steric hinderance of the ortho isomer make it most possibly decrease their tendency to adopt more mobile orientations in cyclodextrin-based complex as meta and para isomers do, resulting in gel formation. FindingsHerein, we report a novel, facile and environmentally-friendly protocol on the recognition of ortho benzene isomers using α-cyclodextrin through host–guest crystalline self-assembly. Visual recognition of ortho-xylene is achieved through amplifying the structural difference of xylene isomers at molecular scale into macroscopic scale. We believe this work unveils subtle rules to control macroscopic assemblies at the molecular level and highlights the potential of using macrocyclic compounds to improve the quality and reduce the energy bill for separation in petrochemical industry.

Synthesis of pH-sensitive benzothiazole cyanine dye derivatives containing a pyridine moiety at the meso position

Four benzothiazole-derived pentamethine cyanine dyes were synthesized with a pyridine moiety at the meso-position of the methine chain with a reaction yield of 89–93%. These dyes were prepared with high purity in a three-step synthesis as prospective pH-responsive probes. Each compound absorbed and fluoresced between 630 and 670 nm within the far-red range of the visible spectrum with high molar absorptivity values calculated between 134,910 L mol −1 cm−1 and 163,816 L mol −1 cm−1 and quantum yields between 9% and 17%. When a 20 μM solution of dye derivatives are exposed to hydrochloric acid in the range of pH 5–6 in ethanol, all the dyes experienced a blueshift in absorbance and emission as well as a decrease in spectral intensity that enables them to operate as pH probes. These properties were further validated via computational studies showing pyridine's influence on each molecules' spectral properties, and pathways for electron delocalization in the presence and absence of acid were proposed. © 2021 Elsevier Science. All rights reserved.

Thioether linked meso functionalized BODIPY DYEmer

Thioether linked meso BODIPY DYEmer 3 was synthesized by two different routes. The reaction of dipyrrothioketone 1 and 8-chloro BODIPY 2 in the presence of triethylamine followed by complexation with BF[Formula: see text] resulted in thioether linked meso functionalized BODIPY DYEmer 3. Using another route, the reaction of 8-chloro BODIPY 2 with sodium hydrosulphide (NaSH) at room temperature resulted in the thioether linked meso BODIPY DYEmer 3. The DYEmer 3 was characterized by 1H, [Formula: see text]C, [Formula: see text]B, [Formula: see text]F NMR, HRMS, and single crystal X-ray crystallography. The properties of DYEmer 3 was compared with the previously reported thioether linked [Formula: see text] and [Formula: see text] BODIPY DYEmers 4 and 5. The structural parameters indicating the intramolecular arrangements of two BODIPY units of DYEmer were compared and corelated with the observed properties. The time-dependent DFT (TD-DFT) calculations suggested that the thioether group at meso position of BODIPY 3 stabilizes the LUMO energy than 8-chloro BODIPY 2. Compared to 8-chloro BODIPY 2 the HOMO-1 of DYEmer 3 is destabilized whereas the LUMO+1 is stabilized.

Sensitive and Visual Detection of Phosgene by a TICT-Based BODIPY Dye with 8-(o-Hydroxy)aniline as the Active Site.

Phosgene and its substitutes (diphosgene and triphosgene) are widely utilized as chemical industrial materials and chemical warfare agents and pose a threat to public health and environmental safety due to their extreme toxicity. Research efforts have been directed to develop selective and sensitive detection methods for phosgene and its substitutes. In this paper, we have prepared two BODIPY-based fluorescent probes, o-Pah and o-Pha, which are two isomers with different active sites, ortho-aminohydroxy (3',4' or 4',3') phenyls at meso position of BODIPY, and compared their sensing performance toward triphosgene. The probe with o-(4'-amino-3'-hydroxyl), o-Pha, exhibits better sensing performance over the o-(3'-amino-4'-hydroxyl), o-Pah, for instance, a lower limit of detection (LOD) (0.34 nm vs. 1.2 nm), and more rapid response (10 s vs. 200 s). Furthermore, based on the above comparative studies, a red-fluorescence probe o-Phae has been constructed through extending 3,5-conjugation of o-Pha. The probe o-Phae displays rapid response (60 s), high sensitivity to triphosgene (LOD=0.88 nm), and high selectivity for triphosgene over relevant analytes including nitric oxide. Finally, a facile test strip for phosgene was fabricated by immobilizing o-Phae in a polyethylene oxide membrane for sensitive (<2 ppm) and selective detection of phosgene in the gas phase.

Rapid Ortho-to-para Nuclear Spin Conversion of H2 on a Silicate Dust Surface

Abstract The H2 molecule has two nuclear spin isomers, the so-called ortho and para isomers. Nuclear spin conversion (NSC) between these states is forbidden in the gas phase. The energy difference between the lowest ortho and para states is as large as 14.7 meV, corresponding to ∼170 K. Therefore, each state of H2 differently affects not only the chemistry but also the macroscopic gas dynamics in space; thus, the ortho-to-para abundance ratio (OPR) of H2 has significant impacts on various astronomical phenomena. For a long time, the OPR of nascent H2 upon formation on dust grains has been assumed to have a statistical value of 3 and to gradually equilibrate in the gas phase at the temperature of the circumstances. Recently, the NSC of H2 was experimentally revealed to occur on water ice at very low temperatures and thus incorporated into gas–dust chemical models. However, H2 molecules should form well before dust grains are coated by water ice. Information about how the OPR of H2 behaves on bare silicate dust before ice-mantle formation is lacking. Knowing the influence of the OPR of H2 is desirable, if the OPR changes even on a bare silicate surface within an astronomically meaningful timescale. We report the first laboratory measurements of the NSC of H2 physisorbed on amorphous silicate (Mg2SiO4) at temperatures up to 18 K. The conversion was found to occur very rapidly.

Action spectroscopy of deprotomer-selected hydroxycinnamate anions

Tandem ion mobility mass spectrometry-coupled laser excitation is used to record photodetachment, photoisomerization and photodepletion action spectra for a series of deprotomer-selected hydroxycinnamate anions, including deprotonated caffeic, ferulic and sinapinic acids. This molecular series accounts for most hydroxycinnamic moieties found in nature. Phenoxide deprotomers for para and ortho structural isomers have similar photodetachment action spectra that span the 350 – 460 nm range with the maximum response occurring between 420 and 440 nm. None of the phenoxide deprotomers showed evidence for E $$\rightarrow $$ Z photoisomerization. In contrast, photoexcitation of the carboxylate deprotomers of caffeic and ferulic acids and the meta-phenoxide deprotomer of caffeic acid initiates intramolecular proton transfer to give the para-phenoxide deprotomer. Photoexcitation of the carboxylate deprotomer of sinapinic acid and ortho-coumaric acid does not result in intramolecular proton transfer, presumably due to substantial barriers for rearrangement. For deprotonated meta-coumaric acid, interconversion between the phenoxide and carboxylate deprotomers occurs in the ion mobility spectrometer drift region where the effective ion temperature is $$T_{eff}\approx $$ 299 K.

Tuning the Regioselective Functionalization of Trifluoromethylated Dienes via Lanthanum-Mediated Single C-F Bond Activation.

The development of new fluorine-containing building blocks and their efficient synthetic access is currently a challenging research field. Herein, the highly regio- and stereoselective addition of a large range of aldehydes onto trifluoromethylated benzofulvenes was achieved using a simple La/I2 /DIBAL-Cl system via a selective C-F bond activation process. This versatile methodology provided homodienyl alcohols bearing a terminal CF2 -alkene with potential further applications, as shown by the dehydration to the first benzofulvenes carrying a difluorovinyl group. In addition, for certain electron-poor aldehydes, unprecedented ipso substitution of the CF3 group in a diene was observed, which, according to DFT studies, is related to the presence of the large, Lewis-acidic lanthanum metal.

Differentiation of bisphenol F diglycidyl ether isomers and their derivatives by HPLC-MS and GC-MS\u2014comment on the published data

Positional isomers of bisphenol F diglycidyl ether (BFDGE) have been analyzed by high-pressure liquid chromatography-mass spectrometry and by gas chromatography-mass spectrometry (HPLC-MS, GC-MS). Positional isomers of BFDGE derivatives (BFDGEx2H2O, BFDGExH2OxHCl) have been analyzed by HPLC-MS. On the basis of the obtained fragmentation patterns, the elution order of the isomers has been unequivocally determined, in standard solutions and in the sample of liquid obtained after rinsing an empty mackerel fish can with acetonitrile. Under HPLC condition, para,para isomers are eluted first, then ortho,para isomers’ elution follows, and ortho,ortho isomers are eluted last. Under GC condition, the reverse elution order has been obtained. For the first time, two ortho,para isomers of BFDGExH2OxHCl have been detected and their elution order has been determined. The obtained results are of key importance for determination of the isomer distribution of BFDGE and its derivatives in food samples.

Near‐Infrared Emission by Tuned Aggregation of a Porphyrin Compound in a Host–Guest Light‐Emitting Electrochemical Cell

AbstractThe synthesis of 5,10,15,20‐tetrakis((5,10‐bis((2‐hexyldecyl)oxy)dithieno[3,2‐c:3′,2′‐h][1,5]naphthyridin‐2‐yl)ethynyl)porphyrin zinc(II) (Por4NT), a near‐infrared (NIR) emitting compound, comprising a zinc porphyrin core linked with triple bonds through its meso positions to four 5,10‐bis((2‐hexyldecyl)oxy)dithieno[3,2‐c:3′,2′‐h][1,5]naphthyridine (NT) arms is reported. Por4NT featured high solubility in common non‐polar solvents, which is ideal for easy processing through solution techniques, and high photoluminescence (PL) efficiency of ≈30% in dilute toluene solution. It also exhibited a strong tendency for aggregation because of its flat conformation, and this aggregation resulted in a strong redshifted emission and a drop in PL efficiency. A well‐matched PBDTSi‐BDD‐Py “host” terpolymer is therefore designed, which is capable of mitigating the aggregation of the Por4NT “guest”. An optimized blend of the host, guest, and an ionic‐liquid electrolyte is utilized as the active material in a light‐emitting electrochemical cell (LEC), which delivered strong NIR radiance of 134 µW cm‐2 with a long wavelength maximum at 810 nm at a low drive voltage of 5.0 V. The attainment of the strong NIR emission from the host–guest LEC is attributed to a tuned aggregation of the Por4NT emitter, which resulted in the desired aggregation‐induced redshift of the emission at a reasonably retained efficiency.

Influence of the haloaryl moiety over the molecular packing in N-phenacylbenzimidazoles crystallizing in the same space group

In this study, a family of N-phenacylbenzimidazoles 1–3 synthesized in high yields (90–93%) by the N-phenacylation reaction of NH-benzimidazole (4) under ultrasonic conditions was recrystallized from the mixture EtOH:AcOEt (1:1 V/V). These compounds crystallize in the same Monoclinic P21/c space group, though the molecular packing is affected by the haloaryl group varying the final crystal structure. The para substitution of the halogen atom in the aryl ring influences a more pronounced electronic deficiency over the methylene bridge allowing the formation of intermolecular C‒H‧‧‧O hydrogen bonds in compounds 1 and 3. Additionally, in compound 2, the ortho substitution of an F atom, not only affects the electron density but also blocks this CH2 group with an intramolecular C‒H‧‧‧O hydrogen bond. Remarkably after the crystallization process, compound 3 crystallizes as a cocrystal with a 4-fluorobenzoic acid molecule obtained by hydrolysis of 3. This co-crystallization affects dramatically the total packing energies from values of -138.7/-135.2 kJ/mol for 1 and 2, respectively, to -229.7 kJ/mol for compound 3.