Search Results (15)

Liquid crystals exhibit unique properties that can be tailored in response to external stimuli. Significant research is directed toward the development of luminescent materials exhibiting liquid crystallinity for various applications. The present work reports Au(I) complexes featuring N-heterocyclic carbene and phenyl acetylide ligands. Metal complexes enable the utilization of the triplet excitons through their inherent spin–orbit coupling, promoting intersystem crossing from singlet (S_n) to triplet (T_n) states to observe room-temperature phosphorescence (RTP). The strong bonds between carbene and Au enhance the thermal stability, and the substituted benzimidazole ring alters the thermodynamic and photophysical properties of the complexes. Incorporating the acetylide ligands with long alkoxy chains led to the formation of liquid crystalline (LC) phases, which exhibited stability over a wide temperature range. Additionally, the luminescence behavior was affected by the ethynyl ligands, and high quantum yields of RTP were observed. This study establishes the development of LC Au(I) complexes with a thermodynamically stable LC mesophase over a wide temperature range for applications in the field of light-emitting functional materials. Full article

The construction of high-performance n-type semiconductors is crucial for the advancement of organic electronics. As an attractive n-type semiconductor, molecular systems based on perylene diimide derivatives (PDIs) have been extensively investigated over recent years. Owing to the fascinating aggregated structure and high performance, S-heterocyclic annulated PDIs (SPDIs) are receiving increasing attention. However, the relationship between the structure and the electrical properties of SPDIs has not been deeply revealed, restricting the progress of PDI-based organic electronics. Here, we developed two novel SPDIs with linear and dendronized substituents in the imide position, named linear SPDI and dendronized SPDI, respectively. A series of structural and property characterizations indicated that linear SPDI formed a long-range-ordered crystalline structure based on helical supramolecular columns, while dendronized SPDI, with longer alkyl side chains, formed a 3D-ordered crystalline structure at a low temperature, which transformed into a hexagonal columnar liquid crystal structure at a high temperature. Moreover, no significant charge carrier transport signal was examined for linear SPDI, while dendronized SPDI had a charge carrier mobility of 3.5 × 10⁻³ cm² V⁻¹ s⁻¹ and 2.1 × 10⁻³ cm² V⁻¹ s⁻¹ in the crystalline and liquid crystalline state, respectively. These findings highlight the importance of the structure–function relationship in PDIs, and also offer useful roadmaps for the design of high-performance organic electronics for down-to-earth applications. Full article

Our research area is related to the spiropyrazolinium-containingcompounds, which are insufficiently studied compared with pyrazoline-containing compounds. Nitrogen-containing azoniaspiromolecules have also been well studied. In drug design and other areas, they are a priori important structures, since rigid spirocyclic scaffolds with the reduced conformational entropy are able to organize a closely spaced area. Azoniaspirostructures are currently of wide practical interest as ionic liquids, current sources (membranes), structure-directing agents in organocatalysis, and in the synthesis of ordered ceramics. Our goal was the synthesis of 2-aminospiropyrazolilammonium chlorides and hexafluorophosphates. Our methodology is based on the tosylation of β-aminopropioamidoximes with six-membered N-heterocycles (piperidine, morpholine, thiomorpholine, and phenylpiperazine) at the β-position. 2-Aminospiropyrazolilammonium chlorides and hexafluorophosphates were obtained by the reaction of double ion substitution in the reaction of toluenesulfonates of 2-aminospiropyrazolinium compounds with an ethereal solution of HCl in ethanol and with ammonium hexafluorophosphate in ethanol in quantitative yields of 55–97%. The physicochemical characteristics of the synthesized compounds and their IR and NMR spectra are presented. The obtained salts were additionally characterized by the single-crystal XRD analysis. The presence of both axial and equatorial conformations of spirocations in solids was confirmed. 2-Aminospiropyrazolilammonium chlorides and hexafluorophosphates have weak in vitro antimicrobial activity on Gram-positive and Gram-negative bacterial lines. Full article

Rare-earth metal sesquioxides (RE₂O₃) are stable compounds that require high activation energies in solid-state reactions or strong acids for dissolution in aqueous media. Alternatively, dissolution and downstream chemistry of RE₂O₃ have been achieved with ionic liquids (ILs), but typically with additional water. In contrast, the anhydrous IL 1-butyl-3-methylimidazolium acetate [BMIm][OAc] dissolves RE₂O₃ for RE = La–Ho and forms homoleptic dinuclear metal complexes that crystallize as [BMIm]₂[RE₂(OAc)₈] salts. Chloride ions promote the dissolution without being included in the compounds. Since the lattice energy of RE₂O₃ increases with decreasing size of the RE³⁺ cation, Ho₂O₃ dissolves very slowly, while the sesquioxides with even smaller cations appear to be inert under the applied conditions. The Sm and Eu complex salts show blue and red photoluminescence and Van Vleck paramagnetism. The proton source for the dissolution is the imidazolium cation. Abstraction of the acidic proton at the C²-atom yields an N-heterocyclic carbene (imidazole-2-ylidene). The IL can be regenerated by subsequent reaction with acetic acid. In the overall process, RE₂O₃ is dissolved by anhydrous acetic acid, a reaction that does not proceed directly. Full article

Aromatic heterocyclic liquid crystal (LC) materials have received much attention from LC chemists for their high birefringence and large dielectric anisotropy, yet few have reported their properties in LC mixtures. In this work, a series of fluorinated benzoxazole liquid crystal compounds were synthesized to evaluate their electro-optical properties in high birefringence LC mixtures, with the expectation of further establishing the theoretical basis and experimental evidence for their applications in LC photonics. Firstly, the effects of the lateral fluorine substituent positions on the molecular synthetic yield, mesomorphic and solubility properties were comparatively investigated. Afterwards, we focused on the fluorination effects on the core electro-optical properties, including birefringence, dielectric anisotropy and further investigation of the viscoelastic coefficient of high birefringence LC mixtures. Research results showed that the benzoxazole liquid crystal compounds possess low melting points, wide nematic phase intervals and good solubility by appropriate lateral fluorine substitution, which is beneficial to further improve the electro-optical properties of high birefringence LC mixtures. Meanwhile, the theoretical and experimental results corroborate each other to well reveal the structure–property relationship. This study demonstrates that fluorination would promote promising applications of benzoxazole-terminated liquid crystals in emerging LC optical devices. Full article

The synthesis and thermotropic behaviour of some di-alkyloxy-phenyl-1,2,4-triazolium trifluoromethane-sulfonate salts bearing a seven-carbon atom perfluoroalkyl chain on the cation is herein described. The fluorinated salts presenting a 1,2,4-triazole as a core and differing in the length of two alkyloxy chains on the phenyl ring demonstrated a typical liquid crystalline behaviour. The mesomorphic properties of this set of salts were studied by differential scanning calorimetry and polarized optical microscopy. The thermotropic properties are discussed on the grounds of the tuneable structures of the salts. The results showed the existence of a monotropic, columnar, liquid crystalline phase for the salts tested. An increase in the temperature mesophase range and the presence of two enantiotropic mesophases for the sixteen-atom alkyloxy chain salt can be observed by increasing the length of the alkyloxy chain on the phenyl ring. Full article

We report herein the synthesis and characterization of three heterocyclic curcuminoid ligands and their homoleptic metal complexes with magnesium and copper. Thus, N-methyl-2-pyrrolecarboxaldehyde, Furan-2-carboxaldehyde, and 2-Thiophenecarboxaldehyde were condensed with 2,4-pentanedione-boron trioxide complex. The first N-methyl-2-pyrrole curcuminoid and its Mg(II) complex are reported. All curcuminoid ligands and their corresponding metal complexes were characterized by infrared spectroscopy (IR), liquid state nuclear magnetic resonance (LSNMR), electron paramagnetic resonance (EPR), mass spectrometry (MS) and single crystal X-ray diffraction (SCXRD). The ThiopheneCurc-Cu (9) constitutes the first case of a “conformationally-heteroleptic” complex. The unique six-peaks star arrangement for the ThiopheneCurc ligand derived from the supramolecular description is reported. The metal complexes of FuranCurc-Mg (5) and ThiopheneCurc-Cu (9) have a good antioxidant effect (IC₅₀ = 11.26 ± 1.73 and 10.30 ± 0.59 μM), three and two times higher than their free ligands respectively. Additionally, (5) shows remarkable cytotoxicity against colon cancer adenocarcinoma cell line HCT-15, comparable to that of cisplatin, with a negligible toxic effect in vitro towards a healthy monkey kidney cell line (COS-7). Full article

Three rings 2-hydroxypyridine liquid crystalline compounds have been prepared and fully characterized. The mesomorphic behavior of the prepared compounds has been investigated in terms of differential scanning calorimetry (DSC) and polarized optical microscopy (POM). Moreover, a comparative study between the prepared compounds and previously reported analogs has been discussed in terms of the orientation and position of the mesogenic core, in addition to the direction of the terminal alkyl chains. Furthermore, a detailed computational approach has been studied to illustrate the effect of geometrical and dimensional parameters on the type of the enhanced texture and the mesomorphic range and stability. The results of the DFT study revealed that the orientation of the mesogen could affect the mesomorphic behavior and this has been attributed in terms of the degree of the polarizability of the linking groups. This result has been confirmed by calculation of the net dipole moment and the molecular electrostatic potential that show how the mesogen orientation and position could impact the molecular charge separation. Finally, the effect of the pyridyl group has been also investigated in terms of the calculated aromaticity index and the π-π stacking. Full article

The use of drugs derived from benzothiadiazine, a bicyclic heterocyclic benzene derivative, has become a widespread treatment for diseases such as hypertension, low blood sugar or the human immunodeficiency virus, among others. In this work we have investigated the interactions of benzothiadiazine and four of its derivatives designed in silico with model zwitterionic cell membranes formed by dioleoylphosphatidylcholine, 1,2-dioleoyl-sn-glycero-3-phosphoserine and cholesterol at the liquid–crystal phase inside aqueous potassium chloride solution. We have elucidated the local structure of benzothiadiazine by means of microsecond molecular dynamics simulations of systems including a benzothiadiazine molecule or one of its derivatives. Such derivatives were obtained by the substitution of a single hydrogen site of benzothiadiazine by two different classes of chemical groups, one of them electron-donating groups (methyl and ethyl) and another one by electron-accepting groups (fluorine and trifluoromethyl). Our data have revealed that benzothiadiazine derivatives have a strong affinity to stay at the cell membrane interface although their solvation characteristics can vary significantly—they can be fully solvated by water in short periods of time or continuously attached to specific lipid sites during intervals of 10–70 ns. Furthermore, benzothiadiazines are able to bind lipids and cholesterol chains by means of single and double hydrogen-bonds of characteristic lengths between 1.6 and 2.1 Å. Full article

The synthesis and characterization of a new class of 1,2,4-oxadiazolylpyridinium as a cationic scaffold for fluorinated ionic liquid crystals is herein described. A series of 12 fluorinated heterocyclic salts based on a 1,2,4-oxadiazole moiety, connected through its C(5) or C(3) to an N-alkylpyridinium unit and a perfluoroheptyl chain, differing in the length of the alkyl chain and counterions, has been synthesized. As counterions iodide, bromide and bis(trifluoromethane)sulfonimide have been considered. The synthesis, structure, and liquid crystalline properties of these compounds are discussed on the basis of the tuned structural variables. The thermotropic properties of this series of salts have been investigated by differential scanning calorimetry and polarized optical microscopy. The results showed the existence of an enantiotropic mesomorphic smectic liquid crystalline phase for six bis(trifluoromethane)sulfonimide salts. Full article

In this study, highly adhesive epoxy-based sealing materials for liquid crystal (LC) displays were fabricated using different types of dihydrazides as thermal latent curing agents. Their curing characteristics, mechanical properties, LC contamination levels, and electro-optical characteristics were investigated depending on the chemical structure of dihydrazides. The epoxy-based sealing material containing a dihydrazide derivative with a bulky heterocyclic ring afforded a high heat curing conversion of 90.4%, high adhesion strength of 54.3 kgf cm⁻², and a high elongation of 57.3% due to the relatively low melting characteristic under heat treatment compared to those involving dihydrazides with short aliphatic or aromatic spacers. In addition, the proposed sealing material exhibited an extremely low LC contamination level of 9 µm, which is essential to the successful operation of LC displays. With respect to electro-optical properties of the LC device, it was found that a dihydrazide derivative with a bulky heterocyclic ring afforded a normal voltage-dependent transmittance curve and fast response time due to the prevention of abnormal homogeneous LC alignment. This study developed highly adhesive and robust epoxy-based sealing materials based on the use of dihydrazides as thermal latent curing agents for advanced LC displays. Full article

Tristriazolotriazines (TTTs) with a threefold alkoxyphenyl substitution were prepared and studied by DSC, polarized optical microscopy (POM) and X-ray scattering. Six pentyloxy chains are sufficient to induce liquid-crystalline behavior in these star-shaped compounds. Thermotropic properties of TTTs with varying substitution patterns and a periphery of linear chains of different lengths, branching in the chain and swallow-tails, are compared. Generally, these disks display broad and stable thermotropic mesophases, with the tangential TTT being superior to the radial isomer. The structure–property relationships of the number of alkyl chains, their position, length and structure were studied. Full article

A platinum (II) complex stabilized by a pyridine and an N-heterocyclic carbene ligand featuring an anthracenyl moiety was prepared. The compound was fully characterized and its molecular structure was determined by single-crystal X-ray diffraction. The compound demonstrated high in vitro antiproliferative activities against cancer cell lines with IC₅₀ ranging from 10 to 80 nM. The presence of the anthracenyl moiety on the N-heterocyclic carbene (NHC) Pt complex was used as a luminescent tag to probe the metal interaction with the nucleobases of the DNA through a pyridine-nucleobase ligand exchange. Such interaction of the platinum complex with DNA was corroborated by optical tweezers techniques and liquid phase atomic force microscopy (AFM). The results revealed a two-state interaction between the platinum complex and the DNA strands. This two-state behavior was quantified from the different experiments due to contour length variations. At 24 h incubation, the stretching curves revealed multiple structural breakages, and AFM imaging revealed a highly compact and dense structure of platinum complexes bridging the DNA strands. Full article

Gold(I) complexes are some of the most attractive materials for generating aggregation-induced emission (AIE), enabling the realization of novel light-emitting applications such as chemo-sensors, bio-sensors, cell imaging, and organic light-emitting diodes (OLEDs). In this study, we propose a rational design of luminescent gold complexes to achieve both high thermochemical stability and intense room temperature phosphorescence, which are desirable features in practical luminescent applications. Here, a series of gold(I) complexes with ligands of N-heterocyclic carbene (NHC) derivatives and/or acetylide were synthesized. Detailed characterization revealed that the incorporation of NHC ligands could increase the molecular thermochemical stability, as the decomposition temperature was increased to ~300 °C. We demonstrate that incorporation of both NHC and acetylide ligands enables us to generate gold(I) complexes exhibiting both high thermochemical stability and high room-temperature phosphorescence quantum yield (>40%) under ambient conditions. Furthermore, we modified the length of alkoxy chains at ligands, and succeeded in synthesizing a liquid crystalline gold(I) complex while maintaining the relatively high thermochemical stability and quantum yield. Full article