Supramolecular Layer Research Articles

Achieving Stable Orientational Zinc Deposition for Reversible Zinc Anode through Supramolecular Anchoring Mechanism.

Aqueous zinc-ion batteries have been impeded by the hydrogen evolution reaction (HER), uncontrolled zinc dendrites, and side reactions on the Zn anode. In this work, a Zn-polyphenol supramolecular network is rationally designed for stabilizing Zn anodes (ZPN@Zn) even at high current density. Theoretical calculations and experiments show that the zinc-polyphenol supramolecular layer effectively inhibits the hydrogen evolution reaction by capturing water molecules through strong hydrogen bonding networks while also facilitating the rapid replenishment of Zn2+ ions at the interface through supramolecular anchoring. Additionally, it results in preferential deposition of Zn on the (002) plane, thereby contributing to nondendritic and highly reversible Zn plating/stripping behaviors even under high rates. Concomitantly, the ZPN@Zn achieves superior stability of nearly 1200 h at a high current density of 20 mA cm-2 and maintains a high CE efficiency of 99.86% after 3000 cycles at 1 mAh cm-2 and 5 mA cm-2. Remarkably, the full cell assembled with ZPN@Zn and NaV3O8 (NVO) endures 25 000 cycles at 20 A g-1, achieving an impressive performance for the realization of dendrite-free Zn anodes by supramolecular modulation.

Crystal structure and Hirshfeld surface analysis of the salt 2-iodoethylammonium iodide – a possible side product upon synthesis of hybrid perovskites

The title organic–inorganic hybrid salt, C2H7IN+·I−, is isotypic with its bromine analog, C2H7BrN+·Br− [Semenikhin et al. (2024). Acta Cryst. E80, 738–741]. Its asymmetric unit consists of one 2-iodoethylammonium cation and one iodide anion. The NH3 + group of the organic cation forms weak hydrogen bonds with four neighboring iodide anions, leading to the formation of supramolecular layers propagating parallel to the bc plane. Hirshfeld surface analysis reveals that the most important contribution to the crystal packing is from N—H...I interactions (63.8%). The crystal under investigation was twinned by a 180° rotation around [001].

Stable Au(111) Hexagonal Reconstruction Induced by Perchlorinated Nanographene Molecules.

Surface reconstructions play a crucial role in surface science because of their influence on the adsorption and arrangement of molecules or nanoparticles. On the Au(111) surface, the herringbone reconstruction presents favorable anchoring at the elbow sites, where the highest reactivity is found. In this work, we deposited large organic perchlorinated molecules on a Au(111) surface via high-vacuum electrospray deposition. With noncontact atomic force microscopy measurements at room temperature, we studied the molecular structures formed on the surface before and after annealing at different temperatures. We found that a supramolecular layer is formed and that a hexagonal reconstruction of the Au(111) surface is induced. After high-temperature annealing, the molecules are removed, but the hexagonal Au(111) surface reconstruction is preserved. With the hexagonal Au(111) surface reconstruction, a periodic lattice of anchoring sites is formed.

A sulfur-containing Cd(II) coordination polymer assembled from 4-(4-pyridinyl)thiazole-2-thiol: synthesis, crystal structure, properties, and Hirshfeld surface analysis

The 4-(4-pyridinyl)thiazole-2-thiol (HPTT) molecule with biological activities is a sulfur-containing organic ligand. Here, one new sulfur-containing coordination polymer based on HPTT and potassium thiocyanate (KSCN), namely, {[Cd(PTT)(HPTT)(SCN)}n, has been synthesized and characterized by physicochemical methods. The single-crystal X-ray diffraction analyses reveal the compound crystallizes in a monoclinic P21/n space group and features a one-dimensional line structure. The crystal structure is stabilized through intramolecular C–H···N and C–H···S hydrogen bonds and intermolecular N–H···N, C–H···π, and π⋯π interactions, generating a two-dimensional supramolecular layer structure. The interactions are also analyzed using Hirshfeld surface analysis. Moreover, the compound shows a relatively thermal stability and solid-state photoluminescence at room temperature. One new sulfur-containing coordination polymer based on 4-(4-pyridinyl)thiazole-2-thiol and potassium thiocyanate has been synthesized and characterized. The single-crystal X-ray diffraction analyses reveal the compound crystallizes in a monoclinic P21/n space group and features a one-dimensional line structure. The crystal structure is stabilized by hydrogen bonds and π⋅⋅⋅π stacking interactions, generating a two-dimensional supramolecular layer structure. The interactions are also analyzed using Hirshfeld surface analysis.

Syntheses, structures, and characterization of two new Zn(ii)/Cd(ii) complexes with phenanthroline derivative

Abstract Under hydrothermal conditions, two novel Zn(ii)/Cd(ii) complexes [Cd2(L)4(Cl)2]·(SO4) (1) and {[Zn2(L)2(Sip)(OH)]·H2O} n (2) (L = 2-(2,6-dichlorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, NaH2Sip = 5-sulfoisophthalic acid monosodium salt) were successfully synthesized and characterized by elemental analysis, single-crystal X-ray diffraction, and Hirshfeld surface analysis. The study reveals that complex 1 is constructed from the binuclear [Cd2L4Cl2] unit, and the [Cd2L4Cl2] units are linked via C–H⋯π and C–Cl⋯π interactions into 2D supramolecular layers. These 2D layers are further connected to generate 3D structures by N–H⋯O and N–H⋯S hydrogen bonds. Complex 2 exhibits a 1D double-chain structure consisting of a binuclear [Zn2L2(OH)] unit, which is further connected by π–π interaction to shape a 2D supramolecular structure.

Syntheses and properties of seven 3,4-dichlorobenzoate-based zinc-rare earth heterometallic complexes containing a field-induced Zn(II)-Dy(III)-Dy(III)-Zn(II) single-molecule magnet

Under solvothermal conditions of CH3CH2OH and H2O, a series of 3d-4f heterometallic complexes [Ln2Zn2(3,4-DCB)10(2,2′-bpy)2] [Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5), Er (6) and Yb (7), 3,4-DCB = 3,4-dichlorobenzoic acid, 2,2′-bpy = 2,2′-bipyridine] were synthesized by the reactions of Ln(NO3)3·6H2O, Zn(NO3)2·6H2O, 3,4-HDCB, 2,2′-bpy and NaOH. These complexes were characterized by single crystal X-ray diffraction, powder X-ray diffraction (PXRD), Fourier transform infrared (FT-IR) spectroscopy and thermogravimetric analysis (TGA) and differential thermo analysis (DTA). Complexes 1–7 show two types of different zero-dimensional (0D) structures although they have the same molecular formula. Complexes 1–5 are isomorphic, and complexes 6 and 7 are isomorphic. In 1–7, linear tetranuclear clusters are formed from 3,4-DCB connecting Ln(III) and Zn(II). They can be expanded into one-dimensional (1D) supramolecular chains or two-dimensional (2D) supramolecular layers by the intermolecular π–π interactions. The photoluminescent properties of 1, 2, 4 and 5 and the magnetic properties of 3–7 were studied in detail. Complex 5 exhibits an obvious field-induced single-molecule magnet behavior with a Ueff value of approximately 24 K.

Two new Zn(ii) coordination polymers incorporating 2-(2,6-dichlorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline: Synthesis and structure

Abstract Based on phenanthroline derivate ligand and Zn(ii), two novel coordination polymers, namely [Zn(L)(hta)] n (1) and {[Zn2(L)2(dhb)2]·H2O} n (2) (L = 2-(2,6-dichlorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, H2hta = heptanedioic acid, and H2dhb = 3,5-dinitro-2-hydroxybenzoic acid), have been synthesized under the hydrothermal condition. For 1, each hta anion bridges two Zn(ii) atoms in a tridentate mode to shape into a chain structure and through different π–π stacking interactions to form a three-dimensional supramolecular structure. The L ligand of 2 connects two neighbouring Zn(ii) atoms to give a 1D chain, which is further extended into the 2D supramolecular layer.

New in situ generated acylhydrazidate-coordinated complexes: Syntheses, structural characterizations and magnetic properties

The present study reports the successful synthesis of three new magnetic coordination polymers, namely [Mn(BPTH)(H2O)]n (1), [Co(BPTH)(phen)]n (2), and [Co(BPTA)(phen)(H2O)2]n (3), through a solvothermal method (H2BPTH = biphenyl-3,3′,4,4′-tetracarboxyhydrazide, H2BPTA = biphenyl-3,3′,4,4′-tetracarboxylic acid, phen = 1,10-phenanthroline). In compounds 1 and 2, the bishydrazide ligand H2BPTH is formed by in situ acylation of H2BPTA with hydrazine hydrate. All the three title compounds contain M2O2 clusters (M=Mn(1), Co(2) and Co(3)). In compound 1, the amido-oxygen atoms O1 coordinate with Mn2+ to form a Mn2O2 cluster, while the adjacent Mn2O2 cluster is interconnected by the ligand's oxygen atoms O3 and O4, resulting in an infinite expansion into a 3D network structure. Compound 2 exhibits a 1D chain structure containing Co2O2 clusters, which further extends into a 2D supramolecular layer through π···π stacking interactions. Compound 3 comprises adjacent Co2O2 clusters interconnected by oxygen atoms O1, O2, and O5 on the ligand to form a 2D layered architecture. The 2D layers are linked through intermolecular O–H···O hydrogen bonds of H2BPTA ligands to form a 3D supramolecular network. Magnetic measurements reveal weak ferromagnetic behavior for compound 1 while compounds 2 and 3 exhibit weak antiferromagnetic interactions at different temperatures. Overall, this research presents new insights into the design and synthesis of coordination polymers with diverse structures and magnetic properties.

New Cyanostyrylcopillar[5]arene Derivative: Synthesis, Photophysical Study, Chromogenic Detection of Aliphatic Amines, and Biofilm-Antibiofilm Activity.

The synthesis, characterization, and application of a new cyanostyrylcopillar[5]arene 1 is reported. Single-crystal X-ray diffraction and other spectroscopic techniques confirm the identity of the new copillar 1. The X-ray diffraction study reveals that the copillar 1 exhibits a 1D supramolecular chain in the solid state involving π···π interactions along the crystallographic c-axis and 1D chains are further connected by interchain C-H···π interactions to establish 2D supramolecular layers within the crystallographic bc-plane. 2D supramolecular chains on further packing introduce a 3D structure with void spaces filled with hexane molecules. Through minimal deviation in the dihedral angle, the cyano-substituted ethylenic group in 1 shows a conjugation with the phenolic -OH, favoring intramolecular bond conjugation (ITBC) and colorimetrically detects the aliphatic amines over aromatic amines in CH3CN. Among the aliphatic amines, tertiary amines are differentiated from primary and secondary amines by the naked eye through color change. Both in solution and solid states, 1 displays vapor phase detection of volatile aliphatic amines. Antibacterial activity analysis shows that while 1 exhibits the antibiofilm action against Gram-positive pathogenic bacteria, Staphylococcus aureus, it promotes biofilm formation by Gram-negative pathogenic bacteria, Pseudomonas aeruginosa.

Structures, photoluminescence, and magnetism of 1D lanthanide coordination polymers dominated on 3,5‐dichlorobenzoate

AbstractTwo series of novel coordination polymers (CPs), namely, Ln3(3,5‐DCB)9(bipy) (H2O)2·(bipy) [Ln = Nd (1), Sm (2)] and Ln2(3,5‐DCB)6(bipy)H2O [Ln = Eu (3), Gd (4), Tb (5) and Dy (6)], have been synthesized by hydrothermal reaction of a bridging ligand, 3,5‐dichlorobenzoic acid (3,5‐HDCB), with LnCl3·nH2O and N‐donor neutral ligand, 2,2′‐bipyridine (bipy). Single‐crystal x‐ray diffraction, elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), and powder x‐ray diffraction (PXRD) for 1–6 are presented. CPs 1 and 2 exhibit trinuclear lanthanide architectures, in which the center Ln(III) are seven‐coordinated and eight‐coordinated adopting monocapped triangular prismatic, distorted square antiprism and bicapped trigonal prismatic coordination geometry, respectively, whereas CPs 3–6 are isostructural dinuclear structures. The center Ln(III) ions are also seven‐coordinated and eight‐coordinated with different coordinate modes adopting distorted monocapped triangular prismatic and square antiprism coordination geometry. Trinuclear CPs 1 and 2 are packed together via hydrogen‐bonding interaction to form the two‐dimensional (2D) supramolecular layers. CPs 3–6 exhibit 2D layers by the π–π interaction. CPs 2, 3, 5, and 6 display the characteristic fluorescent emissions of Sm(III), Eu(III), Tb(III), and Dy(III), respectively. CPs 1 and 4–6 exhibit corresponding weak anti‐ferromagnetic and ferromagnetic interactions of Nd(III), Gd(III), Tb(III), and Dy(III) in the low‐temperature range.

Bis(diisobutylammonium) tetrachloridobis[3-(trifluoromethyl)phenyl]stannate

The asymmetric unit in the title salt, (C8H20N)2[SnCl4(C7H4Cl2F3)2], features a di-isobutylammonium cation in a general position and a diorganotin tetrachloride dianion, i.e. tetrachloridobis(3-trifuoromethylphenyl)stannate(IV), located on a centre of inversion; the SnIV atom is octahedrally coordinated. In the crystal, charge-assisted N+—H...Cl hydrogen bonds along with C—H...F contacts occur within supramolecular layers that interdigitate along the a-axis direction.

A Double-Layer Polysaccharide Hydrogel (DPH) for the Enhanced Intestine-Targeted Oral Delivery of Probiotics

Transplantation of probiotics to the intestine can positively regulate the gut microbiota, thereby promoting the immune system and treating various diseases. However, the harsh gastrointestinal environment and short retention time in the gastrointestinal tract significantly limit the bioavailability and intestinal colonization of probiotics. Herein, we present a double-layer polysaccharide hydrogel (DPH) in the form of a double-layer structure composed of a carboxymethyl cellulose (CMCL) supramolecular inner layer and a dialdehyde alginate (DAA) cross-linked carboxymethyl chitosan (CMCS) outer layer. This double-layer structure allows DPH to encapsulate and deliver probiotics in a targeted manner within the body. In the stomach, the cage structure of the DPH is closed, and the outer layer absorbs surrounding liquids to form a barrier to protect the probiotics from gastric fluids. In the intestine, the cage structure opens and disintegrates, releasing the probiotics. Thus, DPH endows probiotics with excellent intestine-targeted delivery, improved oral bioavailability, enhanced gastrointestinal tract tolerance, and robust mucoadhesion capacity. The encapsulated probiotics exhibit almost unchanged bioactivity in the gastrointestinal tract before release, as well as improved oral delivery. In particular, probiotics encapsulated by DPH exhibit 100.1 times higher bioavailability and 10.6 times higher mucoadhesion than free probiotics in an animal model 48 h post-treatment. In addition, with a remarkable ability to survive and be retained in the intestine, probiotics encapsulated by DPH show excellent in vitro and in vivo competition with pathogens. Notably, DAA-mediated dynamic crosslinking not only maintains the overall integrity of the hydrogels but also controls the release timing of the probiotics. Thus, it is expected that encapsulated substances (probiotics, proteins, etc.) can be delivered to specific sites of the intestinal tract by means of DPH, by controlling the dynamic covalent crosslinking.

Catena-Poly[[di-aqua-bis-(1,3-di-hydro-3-oxo-isobenzo-furan-1-acetato)-copper(II)]-μ-N,N'-(ethane-1,2-di-yl)dinicotinamide

The title compound, {[Cu(C10H7O4)2(C14H14N4O2)(H2O)2]n, contains octa-hed-rally coordinated CuII ions ligated by two bis-(1,3-di-hydro-3-oxo-1-isobenzo-furan-acetate (dibf) ligands and two trans water mol-ecules, linked by N,N'-(ethane-1,2-di-yl)dinicotinamide (edn) ligands into mono-periodic coordination polymer chains. The dibf ligands exhibit a pseudo-mirror positional disorder over two positions in a 89.2 (3)/10.8 (3) ratio; the central amide groups of the edn ligands are disordered pseudo-rotationally in the same ratio. These mono-periodic chain motifs are held into supra-molecular di-periodic supra-molecular layers by means of N-H⋯O hydrogen bonding between edn amide groups and unligated dibf carboxyl-ate O atoms. In turn, the supra-molecular layers are held by crystal packing forces into the full crystal structure of the title compound.

Electron-enriched supramolecular PDI-SiO2 promoting PDS activation for enhanced photocatalytic advanced oxidation

The efficient activation of peroxydisulfate (PDS) for wastewater treatment remains a great challenge. Photocatalysis, which generates highly-reactive electrons and holes, shows great potential in activating PDS for effective degradation and deep mineralization. Herein, an electron-enriched PDI-SiO2 photocatalyst was synthesized by covalently linking 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) onto silicon dioxide (SiO2) to form π-π stacked supramolecular PDI layers for efficient PDS activation. The highly dispersed PDI generates electron-enriched PDI·- under visible light, promoting the rapid activation of PDS for bisphenol A (BPA) degradation. The PDI-SiO2 activated PDS system realized a high BPA degradation rate of 0.100 min−1 and a remarkable mineralization rate of 81%. Moreover, the charge separation efficiency is significantly improved since the electrons of PDI·- are captured by PDS, boosting oxidative degradation and improving the mineralization efficiency. This work developed a novel PDS activation strategy by constructing electron-enriched photocatalyst, and revealed the mechanism of photocatalytic activation and deep mineralization.

The on-Surface Supramolecular Chemistry of Porphyrins, Phthalocyanines and Sub-Phthalocyanines: How Shape and Functionalization Change the Game

By their role in biochemistry, porphyrins have played a central role for “Chemistry beyond the molecule”, long before the term ‘supramolecular chemistry’ has been coined. It is interesting that the bio-chemical functions of porphyrins predominantly derive from the center metal atom, its coordination shell and the coordination-site specific properties. The integration of porphyrins into bio-molecules is safeguarded by covalent chemistry and not ‘supra-molecular’ as such. Nevertheless, square planar porphyrins and pthalocyanines take a decisive role in the development of on-surface supra molecular chemistry: This for their excellent stability and for the many ways they can be functionalized with ligands. Thereby, porphyrin and phthalocyanine chemistry paved the way towards the systematic investigation of many different functional groups known to direct self-assembly and their influence on the formation of on-surface supramolecular layers and chains. I will review the results of on-surface supramolecular assembly experiments performed at the solid-vacuum interface with CN-[1], CN-phenyl, alkoxy [1], fluoro [2] and fluorophenyl [3] and di-methylene-aniline derived functional groups and discuss the supramolecular ordering in terms of estimated binding energies and formation kinetics. It is also interesting to compare the supramolecular ordering in fluids with the constrained ordering of molecules confined to surface substrates. Further insight into the directing power of the individual functional groups derives from a fresh look at the three-fold symmetric pyramidal sub-Phthalocyanines.Fig. 1) Supramolecular ordering of substituted porphyrins in networks fromed by CN-phenyl interaction: a) and b) show higher magnification micrographs of c) and d) in two different imaging modes emphasizing the pi orbitals (HOMO) and the alkyl substituants, respectively. e) shows the dynamicity of a network from sterically more demanding alkyl-phenyl substituents. (for further details see [1] and references therein)[1] N. Wintjes et al. J. Am. Chem. Soc. 2010, 132, 7306–7311[2] J. Girovsky et al. Nature Communications 2017 8:15388[3] S. Nowakowska et al. ACS Nano 2018, 12, 768−778. Figure 1

Insight on the presence of dimethylammonium cation within anionic metal-organic supramolecular host: structural, Hirshfeld surface, optical and theoretical analysis

A new supramolecular metal-organic complex, [(DMA)+{Fe(IDA)2}-] (where H2IDA = iminodiacetic acid and DMA = dimethylammonium cation) (1), has been synthesized solvothermally at 90 °C from reaction of ferric(III) chloride hexahydrate with nitrilotriacetic acid (H3NTA) in stoichiometric ratio. The complex was characterized by single crystal X-ray diffraction (SCXRD) along with spectroscopic analyses. During the reaction process, H3NTA is degraded into IDA2- ligand. Structural analysis reveals that 1 is mononuclear and crystallizes in the monoclinic space group C2/c. Within the [Fe(IDA)2]- unit, Fe3+ shows six-coordinate distorted octahedral geometry. The [Fe(IDA)2]- units are connected by strong N1-H1···O4 hydrogen bonds to form anionic 2D supramolecular layers which are further connected by weak C-H···O hydrogen bonds to form a 3D metal-organic supramolecular host (MOSH) structure having 1D supramolecular channels along the crystallographic c-axis. DMA cations are present within the supramolecular channels through N2-H2···O2 hydrogen bonding interactions. Hirshfeld surface analysis and corresponding 2D fingerprint plots indicate that O···H interactions are the major supramolecular interactions present between MOSH and guest DMA cation. DFT calculations reveal that the HOMO and LUMO of the [Fe(IDA)2]- unit are composed of mixed metal-ligand orbitals. Both the absorption and emission spectra of the complex were studied in aqueous phase and the result was correlated with the TDDFT study.

Construction of Hydrophobic Ammonium Perchlorate with Synergistic Catalytic Effect Based on Supramolecular Self-Assembly for Synchronously Catalyzing the Thermal Decomposition of Ammonium Perchlorate and the Combustion of Aluminum.

Ammonium perchlorate (AP), as an important additive component of composite propellants, is critical to the combustion performance of propellants. Herein, AP@1H,1H,2H,2H-perfluorodecyltrichlorosilane (AP@PF) was prepared by establishing a tannic acid-iron ion (TA-Fe) supramolecular self-assembly layer on the AP surface and connecting the 1H,1H,2H,2H-perfluorodecyltrichlorosilane interfacial layer. Results demonstrate that TA-Fe and 1H,1H,2H,2H-perfluorodecyltrichlorosilane are uniformly bound to the surface layer of AP. AP@PF has a lower high-temperature thermal decomposition peak compared to AP. Meanwhile, the exothermic values of low-temperature thermal decomposition (338 J/g) and high-temperature thermal decomposition (597 J/g) of AP@PF are significantly higher than those of AP. In addition, AP@PF exhibits different surface interfacial properties, such as floating on the water surface and exhibiting a static contact angle of 105° on water. AP@PF shows almost no moisture absorption after aging in humid air for 30 days. The exothermic value of the mixture of AP@PF and aluminum powder (156 J/g) is significantly higher than that of the mixture of AP and aluminum (54 J/g), and the mixture of AP@PF and aluminum powder exhibits a higher calorific value and a stronger emission spectrum. Finally, the synergistic catalytic mechanism of AP@PF on the thermal decomposition of AP and the combustion of aluminum powder is also discussed.

Synthesis, characterization and photocatalytic properties of two Zn(II)-based coordination polymers with 3,5-bis(3,4-dicarboxyphenoxy) benzoic acid

Two new Zn(II) coordination polymers (CPs) with formula [Zn2(HL)·2H2O]n (1), [Zn2(H3L)4(phen)2(H2O)2]n (2) (H5L= 3,5-bis(3,4-dicarboxyphenoxy) benzoic acid and phen = 1,10-Phenanthroline) have been prepared hydrothermally by modulating the nature of chelating N-donor. The assistant ligand effects on the coordination degree of penta-carboxylate and resulted in the formation of the two different 2D 4-connected (43.63) topology and 2D supramolecular layer in 1 and 2, respectively. The two CPs have been used as photocatalysts for photodegradation of dyes exhibit potential photocatalytic properties against pollutants dyes like methyl orange (MO), Rhodamine (Rh B), methyl blue (MB), acid orange (AO) and acid chrome blue (ACB). The potential photocatalytic activity of CP 2 is higher than that of 1. The possible photocatalytic mechanism and variations in the photocatalytic abilities of 2 have also been carried out.

An antibacterial Co(II) mononuclear compound containing N,N-bis(3,5-dichlorosalicylidene)hydrazine obtained from 3,5-dichlorosalicylaldehyde thiosemicarbazone in hydrothermal conditions

A mononuclear compound, [Co(L1)2(H2O)]·2H2O (1), where L1 = N,N-bis(3,5-dichlorosalicylidene)hydrazine, was synthesized under hydrothermal conditions. Note that L1 is derived from the hydrothermal in situ reaction of L2 (L2 = 3,5-dichlorosalicylaldehyde thiosemicarbazone). L2 is prepared by reflux using 3,5-dichlorosalicylic aldehyde and thiosemicarbazide. Although 1 is only a mononuclear structure coordinated with L1, intermolecular hydrogen-bonded interactions between two adjacent mononuclear units creates a 1D supramolecular chain. Furthermore, it self-assembles into a fascinating 2D supramolecular layer via π⋅⋅⋅π stacking between benzene rings of adjacent chains. Hirshfeld surfaces and fingerprint maps of 1 were applied to obtain data on non-covalent interactions. Antibacterial analysis shows that 1 is a potential antibacterial material and the bacteriostasis rate is higher than that of L1 (E. coli: 89.41% for 1, 29.09% for L1; MRSA: 93.17% for 1, 38.54% for L1). The solid and liquid photoluminescence properties of 1 and L1 were also investigated.

(2-Hydroxy-3-Methoxybenzylidene)thiazolo[3,2-a]pyrimidines: Synthesis, Self-Assembly in the Crystalline Phase and Cytotoxic Activity.

A series of new 2-hydroxy-3-methoxybenzylidenethiazolo[3,2-a]pyrimidines with different aryl substituents at the 5 position are synthesized and characterized by 1H/ 13C NMR and IR-spectroscopy and mass-spectrometry, as well as single crystal X-ray diffraction (SCXRD). It was demonstrated that the type of hydrogen bonding can play a key role in the chiral discrimination of these compounds in the crystalline phase. The hydrogen bond of the O-H...N type leads to 1D supramolecular heterochiral chains or conglomerate crystallization in the case of the formation of homochiral chains. The hydrogen bond of O-H...O type gave racemic dimers, which are packed into 2D supramolecular layers with a parallel or angular dimers arrangement. Halogen bonding of the N...Br or O...Br type brings a new motif into supramolecular self-assembly in the crystalline phase: the formation of 1D supramolecular homochiral chains instead 2D supramolecular layers. The study of cytotoxicity against various tumor cells in vitro was carried out. It was found that 2-hydroxy-3-methoxybenzylidenethiazolo[3,2-a]pyrimidines with 3-nitrophenyl substituent at C5 carbon atom demonstrated a high efficiency against M-HeLa (cervical adenocarcinoma) and low cytotoxicity against normal liver cells.