Study on 2D Molecular Networks of Flexible Pentacarboxylic Acid Ligands Induced by Ether Bonds in Response to Selective Guest Inclusion.

The flexibility of ligands allows for their bending, twisting, or rotation to adopt various conformations, leading to distinct symmetries during the self-assembled process. Flexible aromatic acid ligands modified by ether bonds are a promising type of self-assembled module when it comes to surfaces. Here, two pentacarboxylic acid ligands (H5L1 and H5L2) with minor skeleton differences have successfully self-assembled into disparate porous networks on the graphite surface and demonstrated excellent potential for the inclusion of guest molecules. The H5L1 molecule's network structure only accommodates coronene (COR) molecules. With fewer COR molecules, H5L1 molecules act as a host template to accommodate the COR molecules. When there are too many COR molecules, COR molecules will induce H5L1 molecules to transform into a new host-guest nanostructure. Additionally, H5L2 molecules showed the ability to capture C70 molecules and exhibited cavity selectivity. However, the assembled network of H5L2 was slightly deformed in attempts to trap the COR molecules. To understand these phenomena more deeply, various assembled mechanisms were analyzed in combination with building theoretical models and energy analysis. These results reveal the great potential of flexible aromatic acid ligands in two-dimensional self-assembly and host-guest systems for their application in related fields.

Host-Host Interactions Enhanced the Structural Rigidity in a 6-Fold Interpenetrated Diamondoid Metal-Organic Framework Exhibiting C2H2/C2H4 Separation.

Multi-interpenetrated metal-organic frameworks (MOFs) have exhibited excellent performance in selective adsorption due to the variable post-interspersed flexibility, but the design and control remain challenging. Herein, two anthracene-based ligands, 4,4'-(anthracene-9,10-diyl)dibenzoic acid (H2L1) and 9,10-di(pyridin-4-yl)anthracene (L2), are used to construct a new three-dimensional 6-fold interpenetrated MOF [Zn(L1)(L2)]n (NBU-X1), which exhibits multiple C-H···π interactions that enhance the structural rigidity, thereby entangling with a C2H2/C2H4 separation performance. In this material, the incorporation of abundant anthracene rings within the framework not only partitions and restricts the pore window size to a quasi-double pore but also stabilizes it through host-host interactions. The structural stability upon heating or guest displacement/removal has been investigated by single-crystal X-ray diffraction and in situ variable-temperature powder X-ray diffraction, in contrast to the extreme flexibility of most multi-interpenetrated MOFs. The performance of purifying C2H4 from C2H2/C2H4 mixtures has been proved by dynamic breakthrough tests.

Design and construction of hollow metal sulfide/selenide core-shell heterostructure arrays for hybrid supercapacitor.

Transition metal sulfides and selenides are common electrode materials in supercapacitors. However, the slow redox kinetics and structural collapse during charge-discharge cycles of single-component materials have impeded their electrochemical performance. In this study, hollow Co9S8 nanotubes were synthesized through a rational morphology design approach. Subsequently, NiSe2 or Co0.85Se was electrodeposited onto the Co9S8 nanotubes, yielding two core-shell heterostructure arrays, namely, NiSe2@Co9S8 and Co0.85Se@Co9S8. By fully leveraging the advantages and synergistic effects of these dual-phase heterostructures, the NiSe2@Co9S8 and Co0.85Se@Co9S8 configurations demonstrated outstanding areal capacitances of 12.54 F cm-2 and 9.61 F cm-2, respectively, at 2 mA cm-2. When integrated with activated carbon in hybrid supercapacitors, the NiSe2@Co9S8//AC and Co0.85Se@Co9S8//AC devices exhibited excellent energy storage performance, with energy densities of 0.959 mW h at 1.681 mW and 0.745 mW h at 1.569 mW, respectively. Additionally, these hybrid supercapacitors demonstrated remarkable cycling stability, with capacitance retention of 87.5% and 89.5% after 5000 cycles for NiSe2@Co9S8//AC and Co0.85Se@Co9S8//AC, respectively. This study provides a novel approach to the synthesis of multiphase core-shell heterostructures based on metal sulfides and selenides, opening new avenues for future research.

Recent progress in multi-resonance thermally activated delayed fluorescence emitters with an efficient reverse intersystem crossing process.

Multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters have become an active research topic at the forefront of organic light-emitting diodes (OLEDs) owing to their excellent photophysical properties such as high efficiency and narrow emission characteristics. However, MR-TADF materials always exhibit slow reverse intersystem crossing rates (kRISC) due to the large energy gap and small spin-orbit coupling values between singlet and triplet excited states. In order to optimize the RISC process, strategies such as heavy-atom-integration, metal perturbation, π-conjugation extension and peripheral decoration of donor/acceptor units have been proposed to construct efficient MR-TADF materials for high-performance OLEDs. This article provides an overview of the recent progress in MR-TADF emitters with an efficient RISC process, focusing on the structure-activity relationship between the molecular structure, optoelectronic feature, and OLED performance. Finally, the potential challenges and future prospects of MR-TADF materials are discussed to gain a more comprehensive understanding of the opportunities for efficient narrowband OLEDs.

Double charge transfer processes enable a green multiple resonance-induced thermally activated delayed fluorescence emitter for an efficient narrowband OLED.

Benefitting from short-range charge transfer (SR-CT) and through-space charge transfer (TSCT) effects, an efficient green narrowband emitter, BNDCN, was developed. Owing to the synergistic effect of double CT processes, a BNDCN-based organic light-emitting diode showed a high external quantum efficiency of 32.3%.

Design of carbazole-based platinum complexes with steric hindrance for efficient organic light-emitting diodes.

The construction of platinum complexes with high steric hindrance is expected to suppress triple-triplet annihilation and π-π stacking to achieve high-performance organic light-emitting diodes (OLEDs) with low efficiency roll-off. Herein, two large steric hindrance platinum complexes (N-CzPhPtacac and N-CzCF3PhPtacac) were prepared by taking advantage of steric hindrance between the phenyl group on carbazole and the functional group (phenyl and trifluoromethyl substituted phenyl) at the 3-position of a pyridine moiety. Due to the similar electron cloud distribution and gap difference between the HOMO and LUMO, the two complexes showed similar orange-red emission peaks at 590 and 596 nm with high PL quantum yields of 90% and 92% and short excited state lifetimes of 2.77 and 3.08 µs in doped films, respectively. Consequently, OLEDs based on N-CzPhPtacac and N-CzCF3PhPtacac showed maximum external quantum efficiency (EQEmax) values of 15.4% and 18.9%, respectively. Importantly, benefitting from the more stretched spatial configuration from the -CF3 effect, the corresponding OLED exhibited a lower efficiency roll-off, with an EQE of 18.1% at 1000 cd m-2.

A 3D tetrathiafulvalene-based metal-organic framework with intramolecular charge transfer for efficient near-infrared photothermal conversion.

The selection of metal centers can endow donor-metal-accepter (D-M-A) type MOFs with progressive framework dimensions. 3D Cd-based MOFs with intramolecular charge transfer caused by D-M-A exhibit a satisfactory photothermal conversion efficiency of 35.7%, with the temperature rapidly rising from 25 °C to 201 °C in 7 s under 808 nm laser irradiation.

An indolo[3,2,1-jk]carbazole-fused multiple resonance-induced thermally activated delayed fluorescence emitter for an efficient narrowband OLED.

By inserting a tricoordinate B atom into an indolo[3,2,1-jk]carbazole precursor, an efficient fused multiple resonance-induced thermally activated delayed fluorescence emitter was prepared, which exhibits a narrowband emission and a considerable reverse intersystem crossing rate. The corresponding organic light-emitting diode displays an external quantum efficiency of 27.2% with a suppressed efficiency roll-off.

Minor adjustments in the chemical structures of pyridine derivatives induced different co-assemblies by O-H⋯N hydrogen bonds.

The co-adsorption behaviours of aromatic carboxylic acids with various pyridine derivatives were investigated with scanning tunneling microscopy and density functional theory. Surprisingly, minor adjustments in the chemical structures of the pyridine derivatives, such as the relative position of the nitrogen atom or the lengths of the side chains on the backbone would evidently affect the intermolecular O-H⋯N hydrogen bonds and further form various co-adsorption structures.

Effects of functional groups and side chains on assembly of "X"-shaped new aggregation-induced emission molecules.

The self-assembly properties of aggregation-induced emission molecules play important roles in electroluminescence devices and fluorescence sensors because noncovalent interactions in self-assembly structures would accelerate the excitation energy consumption. However, there are only few studies to explore their self-assembly properties on the interface and there is still a great need for further understanding self-assembled mechanisms from the viewpoint of molecular design. Here, we presented three X-shaped aggregation-induced emission molecules X1, X2 and X3, which decorated with different functional groups and alkyl side chains. The self-assembly structures were revealed by scanning tunneling microscopy technique in combination with density functional theory. Results showed that X-shaped molecules self-assembled into different structures, depending on their molecular structure, especially the functional groups. Furthermore, self-assembly structures could be regulated by adjusting solution concentration. In more detail, parallel with gradually increasing solution concentration, the molecules approached closer and molecule-molecule interactions were enhanced, finally resulting in new nanostructures. The self-assembly properties of three X-shaped aggregation-induced emission molecules on the liquid/solid interface would give a guidance for further exploring the aggregation state in three-dimensional space. Meanwhile, the two-dimensional nanostructures might show special properties, which could be used in fabricating next generation functional films.

Self-Assembly of Triphenylamine Macrocycles and Co-assembly with Guest Molecules at the Liquid-Solid Interface Studied by STM: Influence of Different Side Chains on Host-Guest Interaction.

The side chains of macrocyclic molecules have a non-negligible effect on the two-dimensional (2D) supramolecular networks at the liquid-solid interface. In this study, we investigate the self-assembly behaviors of two conjugated triphenylamine macrocycles modified with different alkyl chains and construct the host-guest supramolecular nanopatterns on the highly oriented pyrolytic graphite with a scanning tunneling microscope. In combination with density functional theory calculations, how different side chains affect the host-guest interaction is discussed. This work provides insights into constructing a 2D host-guest dynamic co-assembly on the surface.

Diverse Self-assembly Structures of a Macrocycle Revealed with STM by Adjusting the Solution Concentration.

The macrocyclic molecule [3]C12 TT-TPA was synthesized by a Stille coupling reaction through alternately connecting 4,7-bisthienyl-2,1,3-thienothiazole and triphenylamine units. The concentration-dependent self-assembly structures of [3]C12 TT-TPA were explored in liquid/solid interface by scanning tunneling microscopy and density functional theory. After increasing the solution concentration, five different nanostructures were constructed and the molecular packing densities were gradually enhanced. Those structural transformations from loose structures to compact structures are thermodynamically favourable because those transformations are accompanied by the adsorption of more [3]C12 TT-TPA molecules from liquid phase, which increases the interactions between molecules and the interactions between molecules and substrate considerably. This study of fundamental exploration is important to understand the basic formation mechanisms and the stability of two-dimensional functional materials.

Two-Dimensional Molecular Network Built from Hierarchy Self-Assembly of Perylene Bisimide Derivatives.

The structures of two-dimensional (2D) self-assembled molecular networks formed by a series of perylene bisimide (PBI) derivatives were investigated by scanning tunneling microscopy (STM). By introducing different functional groups to the PBI rings, we successfully built a different self-assembled molecular network on the liquid-solid interface. When the substituent is propanol, PBI is aligned in lines. When we introduced either an ester group or an amide group to the PBI compounds, they tended to form dimers and trimers. Especially, the PBI with the amide groups can form a 2D porous molecular network by hierarchy self-assembly. The 2D porous molecular network has a great potential to be the host molecule for the accommodation of a guest molecule, coronene (COR), and the structure of the 2D porous molecular network can be tuned by varying the concentration. The density functional theory calculations were also performed to disclose the mechanisms involved.

Controlled Construction of an Exquisite Three-Component Co-assembly Supramolecular Structure at the Liquid-Solid Interface.

A three-component supramolecular co-assembly structure formed at the liquid-solid interface by employing a shape-persistent π-conjugated macrocycle (16mer) and two guest molecules (COR and C60) is demonstrated. Scanning tunneling microscopy (STM) observations revealed that 16mer can serve as a versatile host molecule that can co-assemble with both COR and C60 guest molecules to form stable two-component structures, where the COR guest molecule filled in the gap between the side chains of adjacent 16mer molecules, and the C60 guest molecule entered the inner cavity of 16mer. It was found that the adding sequence of COR and C60 guest molecules is crucial to the resulting co-adsorption structure in the three-component system. To obtain the intriguing 16mer-COR-C60 three-component co-assembly structure, the 16mer and COR two-component co-assembly structure should first be constructed on a HOPG surface, followed by addition of C60. Based on the analysis of the STM results and the density functional theory (DFT) calculations, the formation mechanism of the assembled structures was revealed.

Self-assembled flower structures formed by C3-symmetric aromatic carboxylic acids with meta-carboxyl groups.

In this study, two kinds of C3-symmetric hexacarboxylic acids containing three pairs of meta-carboxyl groups self-assembled into similar flower structures with two different sizes of cavities. The bi- and tri-component host-guest systems were built to show no molecular selectivity for the guest molecule COR in the co-assembly process.

Determination of vitamin A in blood serum based on solid-phase extraction using cetyltrimethyl ammonium bromide-modified attapulgite.

Cetyltrimethyl ammonium bromide-modified attapulgite was prepared and utilized as a novel sorbent in a simple solid-phase extraction method for the determination of vitamin A in blood serum. Several factors affecting extraction efficiency were systematically optimized, including the sampling solvent and its volume, as well as the elution solvent and its volume. Under the optimal solid-phase extraction conditions, the adsorption capacity of vitamin A was as high as 28 mg/g according to the Langmuir isotherm model. Based on the developed solid-phase extraction method, the level of vitamin A in 200 µL blood serum sample could be accurately determined by high-performance liquid chromatography. The recoveries of vitamin A spiked in 10% v/v methanol aqueous solutions were in the range of 86.9-92.8%, with the relative standard deviations not more than 8.1%. The method was applied to the determination of vitamin A in serum samples from 20 pregnant women. Compared with the previously reported solid-phase extraction methods for determination of vitamin A in serum, our developed cetyltrimethyl ammonium bromide-modified attapulgite-based solid-phase extraction method used lower serum volume, omitted extra steps (i.e. evaporation and re-dissolution), and eliminated internal standard. The results were promising for it to be used in routine monitoring during pregnancy.

On-Surface Crystallization Behaviors of H-Bond Donor-Acceptor Complexes at Liquid/Solid Interfaces.

Two-dimensional (2D) crystallization behaviors of A-TPC n ( n = 4, 6, 10), T3C4, and hydrogen-bonded complexes T3C4@TPC n ( n = 4, 6, 10) are investigated by means of scanning tunneling microscope (STM) observations and density functional theory (DFT) calculations. The STM observations reveal that A-TPC4, A-TPC10, and T3C4 self-organize into dumbbell-shaped structures, well-ordered bright arrays, and zigzag structures, respectively. Interestingly, T3C4@TPC10 fails to form the cage-ball structure, whereas T3C4@TPC4 and T3C4@TPC6 co-assemble into cage-ball structures with the same lattice parameters. The filling rates of the balls of these two kinds of cage-ball structures depend heavily on the deposition sequence. As a result, the filling rates of the cages in T3C4/A-TPC n ( n = 4, 6) with deposition of T3C4 anterior to A-TPC n are higher than those in A-TPC n/T3C4 ( n = 4, 6) with the opposite deposition sequence. Furthermore, lattice defects formed by T3C4 coexist with the cage-ball structures. Moreover, the similar energy per unit area of lattice defects (-0.101 kcal mol-1 Å-2) and the two cage-ball networks (-0.194 and -0.208 kcal mol-1 Å-2, respectively), illustrating the similar stabilities of lattice defects and cage-ball networks, demonstrates the rationality of lattice defects. Combining STM investigations and DFT calculations, this work could provide a useful approach to investigate the 2D crystallization mechanisms of supramolecular liquid crystals on surfaces.

Self-assemblies of TTF derivatives programmed by alkyl chains and functional groups.

Tetrathiafulvalenes (TTFs) are a class of important functional materials whose intermolecular interaction, which will contribute to constructing a supramolecular structure, still needs further understanding. In this study, the self-assembly behavior and structure of a series of TTFs bearing different alkyl chains and substituents were investigated by scanning tunneling microscopy (STM) in combination with density functional theory (DFT) calculations. Contrary to previous reports, herein, a series of benzoic acid-functionalized TTFs (CnTTFCOOH) and pyridine-functionalized TTFs (CnTTFN) with different lengths of alkyl chains have been substituted on the sulfur atom, where n is equal to 8, 10, 14, or 16. Due to the weak intra- and intermolecular interactions, CnTTFN (n = 8 and 10) molecules cannot be observed during STM scanning. For other cases, various self-assembled monolayers with different nanostructures were observed depending on different substituents. The results reveal that the alkyl chains and functional groups on the TTF skeleton synergistically affect the molecular self-assembly process, which results from the synergism of van der Waals, hydrogen bonding, and SS interactions. These results not only help to explain the relationship between structures and properties, but also help to design better molecular structures for various fields.

A polyethyleneimine-modified attapulgite as a novel solid support in matrix solid-phase dispersion for the extraction of cadmium traces in seafood products.

In current study, a new polyethyleneimine (PEI)-modified attapulgite material was prepared serving as a solid support in matrix solid-phase dispersion for the extraction and determination (by atomic absorption spectrometry) of cadmium in seafood products. The major factors affecting PEI grafting were optimized using various PEI amounts and molecular weights. Parameters pivotal to MSPD extraction efficiency, like: pH, volume of eluting solvent, and the sorbent mass-to-sample ratio were investigated. Quantitative recoveries were achieved with 0.21g of fish sample, 0.13g of PEI-modified attapulgite dispersing agent, and 50% HNO3 eluting solution. The limit of detection and the limit of quantification were found to be 2.5 and 8.3µgkg-1 for cadmium in surimi samples, respectively. The recoveries were in the range of 89.2-100.1%, with RSDs ranged from 3.0% to 7.9% (n = 5). When compared to the method stipulated by the Chinese National Standard GB 5009.15-2014, the newly developed MSPD provides comparable accuracy and even better repeatability for the analysis of the cadmium in real seafood samples.

Crystal structure of ethyl-ene-dioxy-tetra-thia-fulvalene-4,5-bis-(thiol-benzoic acid) 0.25-hydrate.

In the title compound (systematic name: 4,4'-{[2-(5,6-di-hydro-[1,3]di-thiolo[4,5-b][1,4]dioxin-2-yl-idene)-1,3-di-thiole-4,5-di-yl]bis-(sulfanedi-yl)}di-benzoic acid 0.25-hydrate), C22H14O6S6·0.25H2O, the tetra-thia-fulvalene (TTF) core adopts a boat conformation, where the central S2C=CS2 plane makes dihedral angles of 31.34 (4) and 26.83 (6)°, respectively, with the peripheral S2C=CS2 and S2C2O2 planes. In the crystal, the benzoic acid mol-ecules are linked via O-H⋯O hydrogen bonds, forming inversion dimers with R22(8) motifs. The dimers are linked through weak C-H⋯O hydrogen bonds into a chain structure along [-101]. The chains stack along the a axis through S⋯S and S⋯C short contacts, forming layers parallel to the ac plane.