1D Chain Research Articles

2D lattice animal formation in the irreversible aggregation of patchy particles

With the self-assembly of patchy colloids, we can engineer many complex structures. In the present work, we are modeling spherical particles with 2 diagonally opposite patches using the Kern-Frenkel potential coupled with isotropic square well potential having different interaction ranges. The isotropic square well potential formed reversible bonds while the patches were irreversibly bonded. A state diagram is calculated where we observed a range of structures from a 1D chain, 2D planar cluster, and 3D random clusters depending on the width of the patch. These structures are controlled by the number of bonds each patch can form for a given patch angle. The range of the patch width can be analytically calculated using geometric arguments to identify different types of clusters, which agree with our simulations. The aggregation process was diffusion-limited, forming clusters with fractal dimension 2 in the low volume fraction limit, otherwise known as flocculation region, and 2.5 in the high volume fraction limit or percolation region, irrespective of the type of clusters formed. In the flocculation limit of the DLCA aggregation model, we expect a fractal dimension of 1.8, contrary to that, we observed the formation of lattice animals having a fractal dimension of 2. The presence of lattice animals is confirmed using the scaling laws of size distribution and chemical length of the clusters formed in the flocculation limit.

Two novel Zn(II)-thiazolothiazole extended viologen complexes with photochromism, inkless and erasable printing and photo-modulated luminescence

The insertion of conjugated units between the two pyridine rings of traditional viologens is an effective way to regulate the stimulus response. Herein, the rigid thiazolothiazole extended viologen moiety (TTVP, 2,5-bis (pyridinium-4-yl) thiazolo [5,4-d] thiazole propionate) has been utilized in the preparation of photochromic materials, in which two novel complexes {[Zn (TTVP)0.5 (m-HBTC) (H2O)]·DMF·3H2O}n (1) and [Zn(H2O)6]0.5 (p-BDC)0.5·(TTVP)0.5 (2) (m-H3BTC = 1,2,4-benzenetricarboxylic acid, p-H2BDC = 1,4-benzenedicarboxylic acid), have been synthesized and characterized. Structural analysis exhibits that complex 1 features one-dimensional (1D) chain structure, while complex 2 exists as a discrete monomeric structure. As anticipated, both complexes exhibit reversible photochromic properties under UV irradiation because of electron transfer (ET). More importantly, the photo-controlled luminescent properties and the potential application as inkless and erasable printing media are also explored.

Solvation, Hydration, and Counterion Effect on the Formation of Ag(I) Complexes with the Dipodal Ligand 2,6-Bis[(imidazol-2-yl)thiomethyl]naphthalene

A series of new Ag(I) complexes with 2,6-bis[(imidazol-2-yl)thiomethyl]naphthalene (L) and a range of counterions (X−) such as PF6− (1, 2), SbF6− (3), and CF3SO3− (4) was prepared. As shown by SCXRD studies, all of these are 1D coordination polymers with a waved chain motive and general formula {[AgL]X}n. Two methanol solvates containing PF6− (1) and SbF6− (3) counterions are isostructural. The triflate counterion leads to the formation of a topologically equivalent structural motive, with a different conformation of the ligand in the 1D chain and a different crystal packing as a result of the presence of another set of intermolecular interactions. The presence of water in 2 leads to a significant change in the conformation of the ligand. The naphthalene rings show a different orientation towards the imidazole rings, which is energetically less favorable but is stabilized by an extended net of intermolecular interactions with the counterion, which leads to an efficient crystal packing.

Two multifunctional coordination polymers based on 1,4-bis(imidazole-1-ylmethyl) benzene: Synthesis, crystal structure and sensitive detection of enrofloxacin and ciprofloxacin

In this paper, we have successfully obtained two novel compounds, namely, the Cd-based compound [Cd0.5L0.5(BA)(H2O)] n1 (L = 1,4-bis(imidazole-1-ylmethyl) benzene; BA = benzoic acid) and the Co-based compound [Co1.5L1.5(OX)1.5] n2 (H2OX = Oxalic acid) by using the hydrothermal methods. The Cd ion in 1 and the Co ion in 2 have the same coordination number. However, due to the different second ligands, namely benzoic acid in 1 and oxalic acid in 2, 1 is the 1D chain structure and 2 is the 2D layer structure, thus the second ligand also plays an important role in the structure of compound. Two CPs can be used as multifunctional luminescent probes to detect the enrofloxacin and ciprofloxacin with high selectivity and sensitivity.

Improving Photoelectron Localization to Significantly Enhanced Broadband Orange‐Light Emission in Hybrid Antimony Halides with Sb─Cl Secondary Bonding

AbstractHybrid ns2 metal halides have attracted extensive attention due to the unique photophysical behavior. However, the reasonable improvement of photoluminescence efficiency by accurate structural modulation remains a great challenge. Herein, two kind of antimony halides with formulae as (S)/(R)‐[C6H16N2]3[SbCl5]2·2Cl ((S)/(R)‐1·2Cl) and (S)/(R)‐[C6H16N2]2[SbCl5]2 ((S)/(R)‐2) ([C6H16N2]2+ = 1,2‐Diaminocyclohexane) are developed, in which 0D [Sb4Cl20]8− clusters and 1D infinite [SbCl5]n2n− polyanion chains are adopted, respectively. The stoichiometric tunability enables metastable (S)/(R)‐1·2Cl being transformed to dynamic stable (S)/(R)‐2. All compounds contain a large number of Sb─Cl secondary bonds because of the strong chemical activity of 5s2 electrons. The obtained compounds exhibit broadband orange‐light emission, while photoluminescence quantum yield of (S)/(R)‐2 is significantly enhanced to ≈76% due mainly to the generation of more localized electrons onto 1D chains. Experimental and computational results reveal that efficient broadband emission derives from the synergistic emission of singlet and triplet states, where the presence of shallow trap energy levels leads to anti‐thermal quenching behavior. Furthermore, the highly efficient photoluminescence property allows (S)‐2 to become excellent down‐conversion phosphor for white‐light emitting diode. This work proves that exploring structure‐property relationship in hybrid systems is helpful in promoting the rapid development of high‐performance broadband emission metal halides.

Transmission across a ribbon containing a square [formula omitted] impurity

We study the spectrum and transmission coefficient of plane waves propagating along square ribbons of varying widths, containing a square-shaped, PT-symmetric impurity region. We start with a zero-width ribbon (1D chain) and place a PT symmetric dimer. The spectrum is computed numerically and the instability gain is computed as a function of the gain/loss dimer strength. The transmission coefficient is obtained in closed form and examined as a function of wavevector and the gain/loss parameter. Next, we study a ribbon in a narrow ladder configuration containing a square PT impurity. As before, we compute the instability gain numerically and the transmission coefficient in closed form for the two possible input modes. Finally, we repeat the calculations for a wider ladder ribbon containing a Lieb-like impurity in a PT configuration. For all cases and transmission channels, we obtain transmission divergences in wavevector-gain/loss parameter space, whose number increases with the width of the ribbon.

1D Tin(II)‐Based Chiral Hybrid Perovskite Single Crystals with Extremely Distorted Inorganic Chains for Second Harmonic Generation

AbstractThe organic–inorganic hybrid metal halides with chiral structures have attracted great attentions in the field of optoelectronic functional materials, especially for nonlinear optics. To date, second harmonic generation (SHG) properties of several classes of chiral hybrid halides with different metal ions have been reported. However, SHG‐active tin(II)‐based chiral materials are rarely explored, hindering deep understandings of the relationship between their structures and SHG properties. Herein, Sn2+ ions are successfully introduced into chiral hybrid perovskites, and four new species of chiral hybrid perovskites (R/S‐α‐PEA)SnX3 (X = Cl and Br, PEA = phenylethylammonium) are obtained. The as‐grown crystals are in P212121 space group, with highly distorted [SnX6] octahedral units forming 1D chain structures in the lattice, due to the effect of stereochemically active lone pair 5s2 electrons in Sn2+. Such crystals have an SHG response of ≈1.4× Y‐cut α‐quartz for (S‐α‐PEA)SnBr3 and ≈0.9× Y‐cut α‐quartz for (S‐α‐PEA)SnCl3 at 1020 nm excitation, with high polarization ratio of SHG signals as well as wide bandgaps and transparency windows in the meanwhile. This work opens up a new platform for discovering more novel tin(II)‐based chiral perovskites with superior nonlinear optical properties in the future.

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.

Water-stable Cu-based coordination polymer for ratiometric fluorescence detection of riboflavin

Riboflavin was first isolated from milk and widely used in food, biological and pharmaceutical fields. Accurate detection of riboflavin content is of great significance for the treatment of related diseases and the supervision of food/drug quality. In this paper, a 1D chain copper-based coordination polymer with excellent water stability was synthesized by hydrothermal method using rigid ligand 1,10-phenanthroline and flexible ligand 1,4-phenylenedioxydiacetic acid, named Cu-phen-PEDA. Based on the Förster resonance energy transfer (FRET) and dynamic quenching detection mechanism, the emission spectrum of Cu-phen-PEDA overlaps with the absorption spectrum of riboflavin. As an energy donor in this case, Cu-phen-PEDA significantly increases the fluorescence intensity of riboflavin (energy acceptor), while simultaneously decreasing its own fluorescence intensity, which is an effective proportional-building strategy. In the lower concentration range, riboflavin can be specifically recognized by ratiometric fluorescence with a good linear relationship, and the detection limit is as low as 23 nM. The potential aspects of its specificity, stability, reusability and practical application were explored.

Plutonium and Cerium Perrhenate/Pertechnetate Coordination Polymers and Frameworks.

Spent nuclear fuel (SNF) contains transuranic and lanthanide species, which are sometimes recovered and repurposed. One particularly problematic fission product, 99TcO4-, hampers this recovery via coextraction with high valence metals, perhaps by complexation during aqueous reprocessing of SNF. There is limited molecular-level knowledge concerning the coordination chemistry between TcO4- or its well-known surrogate ReO4- and transuranic/lanthanide species. In the current study, we investigated the coordination of ReO4-/TcO4- with plutonium and cerium cations by structural and chemical characterization of a series of isolated extended solids. In this study, Ce represents both trivalent lanthanides and is considered a surrogate for Pu, respectively, in its common trivalent and tetravalent oxidation states. The structural elucidation of the seven isolated crystalline solids revealed that ReO4-/TcO4- directly connects to PuIV, PuVIO22+, CeIII, and CeIV in the terminal and bridging coordination modes, leading to 1-, 2-, and 3-dimensional frameworks. For example, ReO4- coordination to Pu(IV) formed a 1D chain or 2D framework, isostructural with previously isolated Th(IV) compounds. However, PuVIO22+ alternating with ReO4- led to a unique 1D chain, different from the prior-reported U(VI)/Np(VI)-ReO4-/TcO4- structures. Coordination of ReO4-/TcO4- with Ce(III) promotes the assembly of 3D frameworks. Finally, attempted synthesis of a Ce(IV)-ReO4- compound resulted in a 2D framework with a mixed-valence CeIII/IV. The highly acidic reaction conditions supported the reduction of both CeIV and TcVII, challenging isolation of compounds featuring these species. Only one TcO4-containing structure was obtained in this study (CeIII-TcO4 3D framework), vs the six total Ce/Pu-ReO4 compounds. Our three Pu-ReO4 crystal structures are the first reported and translated to atomic-level information about Pu-TcO4 coordination in nuclear fuel reprocessing scenarios, in addition to broadening our knowledge of bonding trends in the early, high-valence actinides.

One-dimensional van der Waals V2Se9 as a conversion-type anode material for advanced Li rechargeable batteries

Volume expansion of active materials during lithium storage is one of the main issues in Li-ion batteries (LIBs) that should be addressed. In particular, large volume changes and particle cracking are problematic for electrode materials based on conversion reaction, which are considered attractive anode materials with high energy densities. In this study, a one-dimensional van der Waals (1D vdW) material, V2Se9, is proposed as a conversion-type anode material for LIBs. The V2Se9 electrode material has a 1D chain molecular structure with vdW interactions between chains to form a bulk crystal structure. The spaces between the 1D chains act as structural buffers and provide short Li+ diffusion paths that can improve the electrochemical performance of the electrode materials. The V2Se9 electrode exhibits a high reversible capacity of 563.3 mAh g−1 at 100 mA g−1 and a high rate capability of 109.1 mAh g−1 at 3200 mA g−1. The capacity retention of V2Se9 electrodes is 83.72% after 100 cycles. Synchrotron X-ray diffraction and X-ray absorption spectroscopy reveal the formation of Li2Se and V metal, indicating that Li ion storage occurs via the conversion reaction. The structural stability of V2Se9 is demonstrated using SEM measurements of the discharged and charged V2Se9 electrodes during cycling. These results demonstrate the reaction mechanism of V2Se9 and highlight the potential of 1D vdW materials as high-performance anode materials in LIBs.

Multifunctional 1D lanthanide-based coordination polymers exhibiting single-chain magnets and fluorescence detection

Given the extensive applications of lanthanide-based materials in optics, electricity, magnetism, biomedicine, and other fields, the strategic development of multifunctional lanthanide-based molecular materials through meticulous design of organic ligands and rational selection of Ln3+ ions with distinct characteristics holds significant importance. In this work, a series of 1D chain lanthanide-based polymers {Ln(L)3(H2O)2}n (Ln = Eu for 1, Gd for 2, Tb for 3, Dy for 4) were successfully synthesized by using monomethyl isophthalate (HL) to control the hydrolysis of Ln3+ ions. Magnetic results revealed a weak paramagnetic interaction in 2, an antiferromagnetic coupling in 3, and an intriguing single-chain magnets behavior in 4. Compound 4 characterized an effective energy barrier of 38.08 K without a direct current field. Additionally, compounds 1, 3 and 4 exhibited photoluminescence behaviors, and the photoluminescence quantum yield (PLQY) of 1 was as high as 56 %. Compound 3 exhibited efficient detection of acetylacetone (acac) and nitroarenes through luminescence quenching, achieving the low limits of detection (LOD) of 0.068 μM for acac, 0.142 μM for Nitrobenzene, 0.260 μM for 4-Chloronitrobenzene and 0.276 μM for p-Nitrobenzoic acid. This study successfully prepared multifunctional lanthanide polymers, incorporating magnetic, optical, and sensing properties, by precisely controlling the hydrolysis of Ln3+ ions using organic ligands. These findings not only enrich the repertoire of multifunctional lanthanide-based materials but also broaden their applications in diverse domains.

Anticancer effect of organotin complexes derived from 2,6-naphthalenedicarboxylic acid by enhancing the ROS generation

Enhancing ROS generation is crucial for anti-metastasis and anti-proliferation effects in anticancer chemotherapeutics. Herein, five organotin complexes [(Ph3Sn)2L] (1) [(R3Sn)2L]n (R = Et 2, R = n-Bu 3), [(n-Bu3Sn)2L(4,4′-bpe)]n (4), [(n-Bu3Sn)2L(4,4′-bipy)]n (5) were synthesized based on appropriate organotin precursors, 2,6-naphthalenedicarboxylic acid (H2L) and auxiliary ligand (4,4′-bipy = 4,4′-bipyridine, 4,4′-bpe = 1,2-di(4-pyridyl)ethylene). It was found that complex 1 exhibits a tetra-coordinated monomeric structure, complexes 2 and 3 show the 2D coordination polymer, and complexes 4 and 5 display the 1D chain with the central tin atoms as all penta-coordinated. These complexes showed high anti-tumor activity in vitro against four cancer cells (A549, HCT116, HepG-2 and HeLa), with IC50 values changed from 0.34±0.01 μM to 25.54 ± 1.55 μM. Additionally, complex 1 could be effective in inhibiting HepG-2 cell migration. Simultaneously, anticancer mechanism studies show that complex 1 induces excessive ROS production in HepG-2 cells, which in turn leads to the occurrence of ROS-induced downstream events, followed by the disintegration of the redox balance, depolarization of mitochondrial membrane potential, nucleus damage and ultimately apoptosis. This work suggests that enhancing the ability of organotin complexes to generate reactive oxygen species and disrupt intracellular redox balance may be a promising anticancer strategy.

Reversible structural change of [Co2Fe2] complexes between diamagnetic hydrogen-bonded 1D chains and paramagnetic complexes within a layered structure of amphiphilic anions.

The combination of amphiphilic ions and metal complexes may enable the construction of assemblies in which the assembly structure and electronic state of the metal complexes change concertedly. In this work, an alternating layered structure of [Co2Fe2] complexes and amphiphilic anions was constructed. In the crystal structure, [Co2Fe2] complexes and water molecules formed a hydrogen-bonded supramolecular one-dimensional (1D) chain in the hydrophilic layer. A reversible structural change between the 1D chain and discrete [Co2Fe2] complexes was found to occur concertedly with an electron transfer-coupled spin transition (ETCST) of the [Co2Fe2] complex and desorption/adsorption of water molecules.

2p–4f one-dimensional chains and two-dimensional networks assembled by a multicoordinating nitronyl nitroxide radical ligand

Two series of 2p–4f complexes, 1D chains and unique 2D networks, were successfully constructed using a multicoordinating nitronyl nitroxide radical. The complex Dy exhibits slow relaxation of magnetization.

A sandwiched Co4-added polyoxometalate for efficient visible light-driven hydrogen evolution.

A new Co4-added polyoxometalate (CoAP) Cs4[(Co(H2O)5)2{(μ2-Co(H2O)4)2Co4(H2O)2(B-α-GeW9O34)2}]·6H2O (1) has been made using a lacunary directing strategy under hydrothermal conditions. Single-crystal X-ray diffraction analysis demonstrated that 1 is a one-dimensional (1D) chain, in which CoAP is linked by cobalt-oxygen octahedra to form a 1D structure with excellent chemical stability. The visible light-driven H2 evolution test demonstrated that 1 has high activity, with an H2 evolution rate of 1485.95 μmol h-1 g-1. PXRD and FT-IR tests demonstrated that compound 1 exhibits excellent heterogeneous catalytic stability.

Tuning the dimensional order in self-assembled magnetic nanostructures: theory, simulations, and experiments.

A major obstacle to building nanoscale magnetic devices or even experimentally studying novel nanomagnetic spin textures is the present lack of a simple and robust method to fabricate various nano-structured alloys. Here, theoretical and experimental investigations were conducted to understand the underlying physical mechanisms of magnetic particle self-assembly in zero applied magnetic field. By changing the amount of NaOH added during the synthesis, we demonstrate that the resulting morphology of the assembled FeCo structure can be tuned from zero-dimensional (0D) nanoparticles to one-dimensional (1D) chains, and even three-dimensional (3D) networks. Two numerical simulations were developed to predict aspects of nanostructure formation by accounting for the magnetic interactions between individual magnetic nanoparticles. The first utilized the Boltzmann distribution to determine the equilibrium structure of a nanochain, iteratively predicting the local deviation angle θ of each particle as it attaches to a forming chain. The second simulation illustrates the differences in nanostructure arrangement and dimensionality (0D, 1D, or 3D) that arise from random interactions at various nanoparticle densities. The simulation results closely match the experimental findings, as seen from SEM images, demonstrating their ability to capture the system's structural properties. In addition, magnetic hysteresis measurements of the samples were performed along two orthogonal directions to show the influence of dimensional order on the magnetic behavior. The normalized remanence (MR/MS||) of the FeCo alloys increases as the dimensions of nanostructures are increased. Of the three cases, the FeCo 3D network structures exhibit the highest normalized nanostructure remanence of 0.33 and an increased coercivity to above 200 Oe at 300 K. This combined numerical and experimental investigation aims to shed light on the preparation of FeCo nanostructures with tailorable dimensional order and it opens new avenues for exploring the complex spin textures and coercive behavior of these multi-dimensional nanomagnetic structures.

Dy/Ho-encapsulated tartaric acid-functionalized tungstoantimonates: heterogeneous catalysts for isoindolinone synthesis.

Two novel rare earth-substituted tungstoantimonates [H2N(CH3)2]8Na12[Dy2(H2O)6(tar)(Sb2W21O72)]2·40H2O (DySbW) and [H2N(CH3)2]6Na14[Ho2(H2O)6(tar)(Sb2W21O72)]2·25H2O (HoSbW) (H4tar = tartaric acid) were synthesized. The meso-polyanions are alternately linked by {Na3(H2O)3} clusters and DL-tar ligands to form 1D chains. Notably, HoSbW exhibits excellent catalytic activity and high stability for the synthesis of isoindolinones using EtOH as a green solvent.

Magnetic properties and magnetocaloric effect of Ln = Dy, Tb carborane-based metal-organic frameworks.

We present the synthesis and magneto-thermal properties of carborane-based lanthanide metal-organic frameworks (MOFs) with the formula {[(Ln)3(mCB-L)4(NO3)(DMF)n]·Solv}, where Ln = Dy or Tb, characterized by dc and ac susceptibility, X-ray absorption spectroscopy (XAS), X-ray magnetic circular dichroism (XMCD) and heat capacity measurements. The MOF structure is formed by polymeric 1D chains of Ln ions with three different coordination environments (Ln1, Ln2, Ln3) running along the b-axis, linked by carborane-based linkers thus to provide a 3D structure. Static magnetic measurements reveal that these MOFs behave at low temperature as a system of S* = 1/2 Ising spins, weakly interacting ferromagnetically along the 1D polymeric chain (J*/kB = +0.45 K (+0.5 K) interaction constant estimated for Dy-MOF (Tb-MOF)) and coupled to Ln ions in adjacent chains through dipolar antiferromagnetic interactions. The Dy MOF exhibits slow relaxation of magnetization through a thermally activated process, transitioning to quantum tunneling of the magnetization at low temperatures, while both compounds exhibit field-induced relaxation through a very slow, direct process. The maximum magnetic entropy changes (-ΔSmaxm) for an applied magnetic field change of 2-0 T are 5.71 J kg-1 K-1 and 4.78 J kg-1 K-1, for Dy and Tb MOFs, respectively, while the magnetocaloric effect (MCE) peak for both occurs at T ∼ 1.6 K, approximately double that for the Gd counterpart.

Magnesium cations as templates for the self-assembly of supramolecular luminescent {Mg@[B18φ34-35]}-clusters.

Solvothermal reaction of magnesium nitrate and boron oxide in N,N-dimethylformamide produced a number of particularly complex supramolecular magnesium borates. Five topologically different types of negatively charged {Mg@[B18φ34-35]}-clusters, φ = O, OH, were observed with the magnesium cation as a core and octadecaborate anions as shells. The clusters assemble via common borate polyhedra forming 1D chains, a 2D mesoporous layer, and 3D mesoporous frameworks with an effective channel width of up to 16 Å. Topological analysis of the clusters in combination with the modular crystallography approach indicates that numerous new functional materials can be obtained by varying their assembly mode. At least one compound containing such clusters exhibits a very strong luminescence.