Alkoxy Chains Research Articles

Fully Non-Fused Ring Electron Acceptors Enable Effective Additive-Free Organic Solar Cells with Enhanced Exciton Diffusion Length.

Low-cost photovoltaic materials and additive-free, non-halogenated solvent processing of photoactive layers are crucial for the large-scale commercial application of organic solar cells (OSCs). However, high-efficiency OSCs that possess all these advantages remain scarce due to the lack of insight into the structure-property relationship. In this work, three fully non-fused ring electron acceptors (NFREAs), DTB21, DTB22, and DTB23, are reported by utilizing a simplified 1,4-di(thiophen-2-yl)benzene (DTB) core with varied alkoxy chain lengths on the thiophene bridge. The material-only costs of these acceptors are only 11-13$ per gram. Importantly, DTB22 has an exciton diffusion length (LD) of up to 25.5nm. The DTB21 and DTB23 exhibit decreased LDs of 20.1 and 23.1nm, respectively. After blending with the polymer donor PBQx-TF, the PBQx-TF:DTB22 film exhibits the fastest hole transfer and the longest carrier recombination lifetime among these OSCs. Consequently, the optimal PBQx-TF:DTB22-based OSC achieves an excellent PCE of 17.00%, which is among the highest values for fully NFREAs. In contrast, the PBQx-TF:DTB21- and PBQx-TF:DTB23-based OSCs show relatively lower PCEs of 15.13% and 15.63%, respectively. Notably, all these OSCs are fabricated using toluene as the solvent, without any additives. Additionally, the DTB22-based OSC also demonstrates good stability, retaining 95% of its initial efficiency after 500 h without encapsulation in a glovebox.

Structural characterisation of a cyanomesogen by X-ray diffraction and computational methods

The work reports the structural analysis of a cyanomesogen namely, p-cyanobenzylidene p-nonyloxyaniline belonging to the Schiff base class of compounds. It exhibits a partial bilayer/inter-digitated smectic Ad phase and a nematic phase. Polarising Optical Microscopy (POM) and Differential Scanning Calorimetry (DSC) studies have been carried out to study phase sequence and transition temperatures. Micro-structural parameters, like molecular length, spacing, crystallite size, activation energy and micro-strain, have been estimated and pair correlation function (PCF) studies have been done for exhibited mesophases using the X-ray diffraction technique. The study investigated the surface, electronic and optical properties of a compound by computational studies like Density Functional Theory (DFT) and Hirshfeld surface analysis (HSA) methods using the DFT B3LYP/6-311++G(d,p) level basis set. The results reveal that the polarity associated with the polar groups and alkoxy chain lengths, contributes majorly to the mesomorphic characteristics and stability. The Highest Occupied Molecular Orbitals (HOMO) and Lowest Unoccupied Molecular Orbitals (LUMO) analyses of the DFT optimised molecule give electronic and geometrical parameters, atomic charge distribution, polarisability factors which are used to interpret the characteristics of the mesophases and their suitability for electro-optical and non-linear optical applications of the compound in terms of the predicted data.

Water-Soluble Lipophilic Near-Infrared Region II Fluorophores for High-Brightness Lipid Layer and Lipid Droplets Imaging Applications.

Fluorescence imaging in the second near-infrared region (NIR-II, 1000-1700nm) has garnered considerable attention for displaying the biological information of deep tissues. However, the lack of biocompatible contrast agents with bright NIR-II emission has hampered the precise clinical application of deep tissue imaging. Here, a lipophilic enhancement strategy employing donor-acceptor-donor (D-A-D) molecules, introducing long alkoxy chains and quaternary ammonium salts for the development of highly bright water-soluble NIR-II fluorophores (BBTD-2C-N), is described. Notably, liposome-encapsulated BBTD-2C-N nanoparticles (B-2C-N/DMPC) in aqueous solution exhibit a 1.8-fold increase in NIR-II fluorescence brightness compared to free BBTD-2C-N in methanol. Avoidance of the aggregation-caused quenching effect and enhanced NIR-II fluorescence are attributed to significantly attenuated π-π stacking interactions and maintained monodisperses in the hydrophobic liposome shell. Moreover, BBTD-2C-N demonstrates superior performance in visualizing lipid droplet-rich HeLa cells in vitro, as well as precise monitoring of adipose tissue and fatty liver in vivo. This study reveals a new avenue for the development of bright NIR-II fluorophores and precise in vivo imaging.

New Molecularly Flexible Self-Assembling Benzothiadiazole Derivatives: Mesomorphism And DFT Investigations

In the present study, we have synthesized symmetric/unsymmetrical BTD embedded self-assembling molecules and investigated for their mesomorphic properties. Two symmetrical series (BTDK-(2-18) and BTDC-(4-18)) comprises benzothiadiazole moiety as a central core unit which is connected to two different systematically varied end-groups, alkoxy ester and alkoxy coumaryl unit connected through ether and imine linkages. On the other hand, the asymmetric molecules have an alkoxy chalconyl unit at one end and a formyl group at the other. It was observed that, the mesomorphism is completely depends on the molecular flexibility. New molecules revealed mesomorphic behaviour with N (nematic), SmA (smectic-A) and SmC (smectic-C) mesophase with high thermal stability and greater range. Changes in mesogenic units (alkoxy ester & alkoxy coumaryl unit) and the impact of altering the alkoxy chain at both ends have been investigated. Interesting evaluation has been carried out on the molecular flexibility which resulted in different mesomorphic behaviour of molecules under study. Furthermore, the experimentally established values of the mesophase thermal stability (Tc) and mesophase temperature ranges (ΔTSmA, ΔTSmC, and ΔTN), as well as the type of the mesophase, were related to the calculated quantum chemical parameters (Frontier molecular orbitals (FMOs), Aspect Ratio, Polarizability, dipole moment, molecular and electrostatic potential (MEP)) that were obtained by using the DFT method of the investigated compounds.

Synthesis, characterization, density functional theory (DFT) analysis, and mesomorphic study of new thiazole derivatives

This study focuses on synthesizing and characterizing a new series of organic compounds with a heterocyclic core based on sulfur (thiazole). These compounds, labeled as N-(4-(4-alkoxyphenyl) thiazol-2-yl)-1-(naphthalen-2-yl) methanimine (ATNM)n, incorporate alkoxy chains of varying lengths (CnH2n+1O, n = 2, 3, 4, 5, 6, 7, 8, 9, 10, and 12) through a multi-step process. Structural analysis using FT-IR, 1H-NMR, and 13C-NMR confirmed the composition of these compounds. Theoretical calculations using density functional theory (DFT) were carried out with the B3LYP 6-311G (d,p) basis set for the entire set of synthesized compounds (ATNM)n. The (Gaussian 9) software was employed to compute optimized geometrical structures of the proposed compounds in the gas phase. However, investigations into their phase behavior using polarizing optical microscopy (POM) and differential scanning calorimetry (DSC) revealed that none of the compounds in this series exhibited the typical mesomorphic characteristics of liquid crystals. Comparisons were made between theoretical predictions from DFT and observed data obtained through synthesized compounds study. The results revealed that the presence of terminal alkoxy significantly influenced the overall energy of potential geometric structures, along with their physical and thermal characteristics. KEY WORDS: Heterocyclic compounds, Thiazole, Liquid crystals, DFT, Methanimine Bull. Chem. Soc. Ethiop. 2024, 38(6), 1827-1842. DOI: https://dx.doi.org/10.4314/bcse.v38i6.25

Structural characterization of nitazene analogs using electron ionization-mass spectrometry (EI-MS)

Nitazene analogs are among the most recent and potent additions to the novel synthetic opioid (NSO) market, and new analogs continue to emerge. Seized drug analysis commonly utilizes gas chromatography-electron ionization-mass spectrometry (GC-EI-MS), so it is therefore imperative to understand how nitazene analogs behave under EI-MS conditions, and how substitution at various sites on the molecule may impact the resulting EI mass spectra. This study characterizes the EI fragmentation behavior of 20 representative nitazene analogs that contain differing substitutions and proposes rational mechanisms to explain the observed behavior.A general EI fragmentation pathway for nitazene analogs was proposed, with the most common nitazene fragment ions being observed at m/z 86, m/z 107, m/z 58, and m/z 77. Characteristic ions were determined for different substitution groups, enabling the identification of diethyl, desethyl, pyrrolidine, and piperidine substitutions at the amine moiety, and different alkoxy chain lengths at the aromatic ring of the benzyl group. Mechanisms for the formation of these characteristic ions were proposed with the aid of isotopically labeled standards and high-resolution mass spectrometry measurements. To help with the interpretation of EI mass spectra for nitazene analogs, decision trees were developed that encompass the characteristic fragment ions observed for substitutions to the amine moiety and benzyl group, with additional criteria provided for substitutions to the benzimidazole moiety. This study summarizes the fragmentation patterns and characteristic fragment ions in the EI mass spectra of 20 representative nitazene analogs, which will aid the seized drug community in identifying novel nitazene analogs.

Tuning the Properties of Hydrazone/Isosorbide-Based Switchable Chiral Dopants.

The long-range supramolecular interactions in liquid crystals (LCs) can be used to amplify and subsequently propagate microscopic structural changes into macroscopic events. Here, we report on a systematic structure-property analysis using 16 chiral photoswitchable dopants composed of bistable hydrazones and chiral isosorbide moieties. Our findings showcase the relationship between the dopant's structure and its helical twisting power (β), and hence, the photophysical properties of the host LC. We show that an increase in the hydrazone CNNH dihedral angle results in an increase in the β value, while alkoxy chains do not lead to such an increase. These results contradict established rules of thumb, stating that structural rigidity and long alky chains are needed for high β values. We also found that the position of the substitution, whether at the 2' or 5' positions of the isosorbide unit, or the attachment of the chiral unit to the rotor or stator phenyl units can have negative or positive additive effects that can either increase or decrease the β values. These results made us hypothesize that unsymmetrically functionalized dopants should result in large Δβ values, which we corroborated experimentally. Moreover, a fluorine-functionalized dopant resulted in higher overall β values, most likely because of π-π interactions. Finally, the dopants were used in modulating and locking in the reflective properties of LC films, yielding multicolor LC canvases that can reflect light from the ultraviolet to the infrared range (i.e., a manipulation of up to ca. 1500 nm of reflected light).

Synthesis, optical properties and self-assemblies of a new halogenated BODIPY dye with long alkoxy chain

A new boron-dipyrromethene (BODIPY) dye modified with two bromine atoms at the 2,6-positions and three hydrophobic p-(dodecyloxy)styryl groups at 3,5,8-positions was designed and synthesized. Its molecular structure was characterized by 1HNMR and MALDI-TOF-MS. The photophysical properties and aggregate behavior of dye 3 in solution were studied by UV–visible absorption and fluorescence spectroscopy. The dye 3 exhibited strong absorption and a high fluorescence quantum yield in different solvents. The self-assembly behaviors were investigated in THF and water mixtures, and the J-aggregates can be formed. Supramolecular self-assembly behavior of dye 3 was confirmed by temperature-dependent UV−Vis absorption. In addition, the self-assembly behavior of dye 3 in liquid-solid interface was studied using scanning tunneling microscopy (STM) and displays highly ordered linear arrangement on HOPG. The self-assembly processes are found to be adjusted by halogen bonding as well as π−π stacking.

Metal-free phenothiazine dyes with alkoxy chains modified at different position for dye-sensitized solar cells

Long alkyloxy or alkoxyphenyl chains are commonly introduced to organic dye sensitizers in dye-sensitized solar cells (DSSCs) to inhibit the aggregation of sensitizer on the TiO2, thereby minimizing charge recombination. Here, we synthesized four D-D-π-A sensitizers (TP-C6, TP-PhOC6, C6O-TP-C6, C6O-TP-PhOC6), that feature alkyl-/alkoxyphenyl- moiety in phenothiazine (PTZ) donor’s N-position, and either alkoxy or no alkoxy groups in triphenylamine (TPA) auxiliary donor. Then, their photophysical, electrochemical and DSSCs properties were investigated. The UV-Vis and electrochemical studies revealed that all four dyes exhibited good light absorption ability and appropriate HOMO-LUMO energy levels. The introduction of alkoxy at the donor or auxiliary donor can result in a significant redshift in absorption. Among them, TP-PhOC6, which incorporates an alkoxy phenyl group at the N-position of PTZ and lacks alkoxy in TPA, induces a greater redshift in ICT absorption with strong absorption intensity. Additionally, in TP-PhOC6 based DSSC, mitigated charge recombination was observed. As a result, this device exhibited the strongest and widest IPCE spectrum, the highest Jsc (12.77 mA/cm²) and Voc (0.85 V), leading to the highest PCE (6.59 %).

Ether chain modified electrochromic polymer based on EDOT and benzene

Polar side chain plays an critical role in regulating molecular aggregation, film morphology and electrochromic properties of conjugated polymer. Here an ether chain modified conjugated polymer poly(EB-ether) based on EDOT and benzene was prepared at low oxidation potential by electrochemical method in EtOH-CH2Cl2 (v/v = 5/1) containing 0.1 M Bu4NPF6. The prepared poly(EB-ether) could achieve similar electrochromic parameters with alkoxy chain modified poly(EB-alkoxy), such as optical contrast of 35 %, response time of 0.8 s, coloration efficiency of 283 C−1 cm2, and reversible color change between dark red and blue. Electrochromic results indicate that high-performance poly(EB-ether) film could be prepared in mixed solvent containing little CH2Cl2. Therefore, the introduction of ether chain in precursor is a feasible method to decrease or avoid the use of halogenated solvent in electrochemical polymerization process of precursor.

Arylazo-3,5-diphenylpyrazole Derivatives: Molecular Probes Exhibiting Reversible Light-induced Phase Transitions for Energy Storage and Direct Photolithographic Patterning.

We report azopyrazole photoswitches decorated with variable N-alkyl and alkoxy chains (for hydrophobic interactions) and phenyl substituents on the pyrazoles (enabling π-π stacking), showing efficient bidirectional photoswitching and reversible light-induced phase transition (LIPT). Extensive spectroscopic, microscopic, and diffraction studies and computations confirmed the manifestation of molecular-level interactions and photoisomerization into macroscopic changes leading to the LIPT phenomena. Using differential scanning calorimetric (DSC) studies, the energetics associated with those accompanying processes were estimated. The long half-lives of Z isomers, high energy contents for isomerization and phase transitions, and the stability of phases over an extended temperature range (-60 to 80 °C) make them excellent candidates for energy storage and release applications. Remarkably, the difference in the solubility of the distinct phases in one of the derivatives allowed us to utilize it as a photoresist in photolithography applications on diverse substrates.

Thermally activated delayed fluorescence dendrimers with strategic dendrons to construct highly efficient solution-processed OLEDs

For the promising merits of the precise molecular structures and the satisfactory dissolvability, Thermally activated delayed fluorescence (TADF) dendrimers are turning into the attractive candidates for fully solution-processed organic light-emitting diodes (OLEDs). However, the rational design of TADF dendrimers with strategic dendrons for improving the efficiency and decreasing efficiency roll-off is still challenging. Here, two TADF dendrimers, (4S,5R)-2,4,5,6-tetrakis(4-((6-((9-(3-(9H-carbazol-9-yl)phenyl)-9H-carbazol-3-yl)oxy)hexyl)oxy)-9H-carbazol-9-yl)isophthalonitrile (G-O-mCP) and (4S,5R)-2,4,5,6-tetrakis(4-((6-(3,5-bis(1-phenyl-1H-benzo[d]imidazol-2-yl)phenoxy)hexyl)oxy)-9H-carbazol-9-yl)isophthalonitrile (G-O-DPBi) were developed and synthesized by integrating the peripheral strategic dendrons with the emissive core through nonconjugated alkoxy chains. Impressively, the peripheral dendron of G-O-mCP possessing the superior hole-transporting capability belongs to the electron-donor category and the peripheral dendron of G-O-DPBi with the admirable electron-transporting capability belongs to the electron-acceptor category. The elaborate regulation of the different dendrons with solubilizing groups is beneficial for restraining the aggregation-caused quenching (ACQ) effect and balancing the carrier transport capability. Consequently, the fully solution-processed device based on G-O-mCP realized the maximum external quantum efficiency (EQE) of 19.98 %. In addition, the formation of the interfacial exciplex endows the solution-processed device with a extremely low turn-on voltage (Von) of 2.7 V and a high power efficiency (PE) of 43.80 lm/W, which is among the highest power efficiency of the reported TADF-OLEDs.

New Series of Hydrogen-Bonded Liquid Crystal with High Birefringence and Conductivity.

Liquid crystals with high dielectric anisotropy, low operational thresholds, and significant birefringence (Δn) represent a key focus in soft matter research. This work introduces a novel series of hydrogen-bonded liquid crystals (HBLCs) derived from 4-n-alkoxybenzoic, 4-alkoxy-3-fluorobenzoic derivatives (nOBAF), 4-alkoxy-2,3-fluorobenzoic derivatives (nOBAFF), and 2-fluoro-4-nitrobenzoic acid. The HBLCs were characterized using Fourier transform infrared spectroscopy, and their thermal behavior was evaluated via differential scanning calorimetry. Optical observations were conducted using polarized optical microscopy. The results indicate that mixtures containing benzoic acid with a bilateral fluorine substituent exhibit both SmA and SmC phases, while those with a unilateral fluorine substituent exhibit nematic and SmA phases. Moreover, an increase in the length of the alkoxy chain results in an expanded mesophase temperature range. This study demonstrates that the presence of a fluorine substituent and the incorporation of an NO2 group in the molecular structure result in an increase in dielectric permittivity, DC conductivity, dielectric anisotropy, and birefringence.

Smart design of highly luminescent octupolar mesogenic tetra styryl-alkynyl bipyrimidine-based chromophores presenting non-linear optical properties

The research investigations reported in this paper focuses on the influence of rational design on the photophysical properties of new all-organic multifunctional chromophores. Nonlinear optical (NLO) behavior, optical properties and mesogenicity of several new π-conjugated octupolar chromophores, presenting alkoxy styryl-alkynyl donor groups carrying aliphatic achiral and chiral chains in the 3,4/3,5/2,4 position, connected to electron-accepting 2,2-bipyrimidine cores are investigated by various techniques (light-transmission measurements, polarized-light optical microscopy, differential scanning calorimetry measurements, two-photon excited fluorescence and Hyper Rayleigh Scattering). The mesogenic properties were investigated depending on the position of the alkoxy chain and the 3,4 derivatives were found to exhibit liquid-crystal properties with the formation columnar phases over large temperature ranges which were confirmed by small-angle X-ray scattering analysis. All the molecules exhibit exceptional high fluorescence quantum yields values around 80 % and excellent nonlinear optical properties.

Responsive Organic Fluorescent Aggregates Based on Ion‐π Interactions Away from Fluorescent Conjugated Groups

AbstractResponsive organic luminescent aggregates have a wide range of application fields, but currently there is still a lack of reasonable molecular design strategies. Introducing ion‐π interactions into molecules can effectively alter their luminescent properties. However, current research typically focuses on ion localization at luminescent conjugated groups with the strong interaction forces. In this work, we introduce the flexible alkoxy chain spacers between fluorescent conjugated groups and ion‐π interaction sites, and then adjust the fluorescence performance of the molecule by changing the strength of ion‐π interactions. Bromine ion‐based molecules with strong ion‐π interactions exhibit high and stable fluorescence quantum yields in crystals and amorphous powders under the external stimuli. Hexafluorophosphate ion‐based molecules with weak ion‐π interactions have the high fluorescence quantum yield in crystals and very low fluorescence quantum yield in amorphous powders, showing variable fluorescence intensities under external stimuli. This demonstrates a new class of responsive organic luminescent solid‐state materials.

Responsive Organic Fluorescent Aggregates Based on Ion-π Interactions Away from Fluorescent Conjugated Groups.

Responsive organic luminescent aggregates have a wide range of application fields, but currently there is still a lack of reasonable molecular design strategies. Introducing ion-π interactions into molecules can effectively alter their luminescent properties. However, current research typically focuses on ion localization at luminescent conjugated groups with the strong interaction forces. In this work, we introduce the flexible alkoxy chain spacers between fluorescent conjugated groups and ion-π interaction sites, and then adjust the fluorescence performance of the molecule by changing the strength of ion-π interactions. Bromine ion-based molecules with strong ion-π interactions exhibit high and stable fluorescence quantum yields in crystals and amorphous powders under the external stimuli. Hexafluorophosphate ion-based molecules with weak ion-π interactions have the high fluorescence quantum yield in crystals and very low fluorescence quantum yield in amorphous powders, showing variable fluorescence intensities under external stimuli. This demonstrates a new class of responsive organic luminescent solid-state materials.

Mesomorphic and optical properties of azo-ester liquid crystalline reactive mesogens with enhanced thermal stability

A series of azo-ester-linked polymerizable liquid crystalline compounds M1-M3, containing lateral methyl substitution and different terminal alkoxy substituents, e.g., −OCH3, −OCH2CH3, and −OCH2CH2CH3 have successfully been synthesized and characterized. The chemical structures of the prepared compounds were confirmed by different spectroscopic techniques. Thermogravimetric analysis revealed that all the compounds exhibited excellent thermal stability and showed two-staged decomposition patterns. The optical microscopic study revealed that all compounds displayed only the nematic phase and lateral substituent played a crucial role in the formation of single mesophase. The broad X-ray scattering peaks for M1, M2, and M3 in the 2.5–5.5 nm−1 region was observed at temperatures of 154 °C, 85 °C, and 129 °C, respectively, upon cooling from the isotropic liquid, confirming the existence of nematic mesophase. The electronic spectra of M1-M3 showed two main absorption bands with λmax ranges of 263–266 and 369–377 nm. The E-Z photoisomerization study of M1-M3 showcased that the processes followed the first-order kinetic, and the isomerization rate decreased as the alkoxy chain length increased. On the contrary, the Z-E thermal isomerization rates for M1-M3 showed insignificant changes as the alkoxy chain length increased.

Coumarin Schiff base derivatives with alkyl 4’-formyl-biphenyl-4-carboxylate: design, synthesis, mesomorphic studies and DFT calculations

ABSTRACT Symmetric and unsymmetric homologous series of coumarin Schiff base derivatives with alkyl 4’-formyl-biphenyl-4-carboxylate have been synthesised and studied for their mesomorphic behaviour. In the symmetric homologous series of Schiff base derivatives BPES(6–16), alkoxy chain length was varied at both ends of the molecules with n = 6,8,10,12,14,16, while in the unsymmetric homologous series of Schiff base derivatives 10BPEU(2–12), chain length was varied at coumarin end only (n = 2–8,10,12). In symmetric homologous series, compounds BPES(6–10) (n = 6,8,10) exhibited enantiotropic smectic A (SmA) mesophase, while smectic C (SmC) mesophase in cooling cycle only. SmC mesophase became prominent on increasing the chain length n = 12,14,16 in BPES(12–16). In the unsymmetric homologous series 10BPEU(2–12), compound with n = 2 showed monotropic nematic mesophase and highly stable (~165 °C) SmA mesophase. Higher analogues in unsymmetric series were turned biphasic and showed SmA as well as SmC mesophase during cooling scan only. Compound with n = 12 showed stable enantiotropic SmC mesophase (~92 °C). VT-XRD analysis of symmetric compound with n = 12, showed the tilted SmC mesophase. Further DFT calculations were investigated for un/symmetric series along with the literature molecules with similar variations and compared for various structural (length, aspect ratio) and electronic (dipole moment, polarisability) parameters to establish correlation with observed mesomorphic behaviour.

Coumarin Schiff base derivatives with 4′-alkoxy biphenyl-4-carboxaldehyde: Synthesis, mesomorphic studies and DFT calculations

Two homologous series of coumarin Schiff base derivatives with 4′-alkoxy biphenyl-4-carboxaldehyde have been designed and synthesized. All the compounds were analyzed IR, 1H NMR, 13C NMR, ESI-MS and CHN analysis followed by mesomorphic properties polarizing optical microscopy (POM) and differential scanning calorimetry (DSC) analysis. In the first homologous series BPS(6–16), Schiff base of 7-alkoxy-3-aminocoumarin with 4′-alkoxy biphenyl-4-carboxaldehyde, alkoxy chain length was varied systematically at both end of the molecules such as n = 6,8,10,12,14,16. In this series, BPS(6–10) (n = 6,8,10) exhibited enantiotropic nematic(N) and smectic C (SmC) mesophase and turned to monophasic on increasing the chain length n = 12,14,16 in BPS(12–16) with stable SmC mesophase. While in the second homologous series 10BPU(2–16), systemic variation of alkoxy chain length was carried out at coumarin end only (n = 2–18) and 4′-decyloxy-biphenyl-4-carboxaldehyde was used for Schiff base formation. In the this series, early member of the series with n = 2,3 showed enantiotropic very stable (∼ 145 °C) nematic mesophase, while N as well as SmC mesophase were observed for n = 4–8 at, whereas with increase of chain length stability of nematic mesophase was decreased and that of SmC was increased. Higher membered analogous 10BPU(12–16) exhibited SmC mesophase with stability in the rage of 130–160 °C. VT-XRD analysis was also confirmed the tilted SmC mesophase in this class of compounds. For both the series, all compounds were studied for the DFT calculations as well as literature molecules with similar variations. Based on the calculated structural (length, aspect ratio) and electronic (dipole moment, polarizability) parameters were correlated with mesomorphic behaviour observed for literature compounds and compounds from both the series followed by the detailed discussion.

Heptagonal Molecular Tiling via Self-Assembly of Heptagonal Phenylene-Ethynylene Macrocycle at the Liquid-Solid Interface.

The molecular-level scrutinization of on-surface tiling garners considerable interest among scientists. Herein, we demonstrate molecular-level heptagonal tiling using the self-assembly of a heptagonal meta-phenylene-ethynylene macrocycle featuring 14 long alkoxy substituents at the liquid-graphite interface using scanning tunneling microscopy. This heptagonal macrocycle produces an antiparallel pattern at the 1-phenyloctane-graphite interface through van der Waals interactions between the alkoxy chains. This pattern resembles the densely packed pattern of heptagonal tiles, albeit with variations in the orientations and spacing of heptagonal cores owing to intermolecular interactions between the alkoxy chains. Conversely, at the 1,2,4-trichlorobenzene-graphite interface, the heptagonal molecule forms an oblique pattern composed of four independent molecular orientations. This phenomenon arises from core distortion induced by the coadsorption of the solvent molecules within the intrinsic macrocyclic pores. This study elucidates the design strategy - specifically, the choice of heptagonal molecular building block - for heptagonal tiling and fills a crucial gap in the field of two-dimensional crystal engineering.