N-doped carbon Co/CoOx with laccase-like activity for detection of epinephrine.

N-doped carbon Co/CoOx with laccase-like activity was directionally designed by pyrolyzing Co-coordination polymer and applied to detect epinephrine, which revealed a new preparation strategy for laccase mimics. The formation mechanism of the N-doped carbon Co/CoOx nanozyme was reconnoitered by a thermogravimetric-mass spectrometry system (TG-MS). N-doped carbon Co/CoOx exhibited outstanding laccase-like activity, and the Michaelis-Menten constant and maximum initial velocity were calculated to be 0.087 mM and 0.0089 µM s-1, respectively. Based on this principle, a simple colorimetric sensing platform was developed for the quantitative detection of epinephrine, which can be used to diagnose pheochromocytoma. In addition, the visual platform for detecting epinephrine exhibited a linear range of 3 to 20 µg mL-1 and a calculated detection limit of 0.42 µg mL-1. Therefore, the proposed colorimetric sensing platform is a promising candidate to be applied in precise early pheochromocytoma diagnosis.

Hydrogen-Bonded Framework of a Cobalt(II) Complex Showing Superior Stability and Field-Induced Slow Magnetic Relaxation.

A unique hydrogen-bonded organic-inorganic framework (HOIF) constructed from a mononuclear cobalt(II) complex, [Co(MCA)2·(H2O)2] (HMCA = 4-imidazolecarboxylic acid), via multiple hydrogen-bonding interactions was synthesized and structurally characterized. The Co(II) center in the HOIF features a highly distorted octahedral coordination environment. Remarkably, the CoII HOIF showed permanent porosity with superior stability as established by combined thermogravimetric analysis (TGA), variable-temperature infrared spectra (IR), variable-temperature powder X-ray diffraction data (PXRD), and a CO2 isotherm. Structural studies reveal that short multiple hydrogen bonds should be responsible for the superior thermal and chemical stability of a HIOF. Magnetic investigations reveal the large easy-plane magnetic anisotropy of the Co2+ ions with the fitted D values being 22.1 (magnetic susceptibility and magnetization data) and 29.1 cm-1 (reduced magnetization data). In addition, the HOIF exhibits field-induced slow magnetic relaxation at low temperature with an effective energy barrier of Ueff = 45.2 cm-1, indicative of a hydrogen-bonded framework single-ion magnet of the compound. The origin of the significant magnetic anisotropy of the complex was also understood from computational studies. In addition, BS-DFT calculations indicate that the superexchange interactions between the neighboring CoII ions are non-negligible antiferromagnetism with JCo-Co = -0.5 cm-1. The foregoing results provide not only a carboxylate-imidazole ligand approach toward a stable HOIF but also a promising way to build a robust single-ion magnet via hydrogen-bond interactions.

Dissolving Graphene/Poly(Acrylic Acid) Microneedles for Potential Transdermal Drug Delivery and Photothermal Therapy.

We developed a composite of graphene and poly(acrylic acid) (PAA) to build dissolving microneedles for potential transdermal drug delivery and photothermal therapy. The results showed that each microneedle array comprised 100 (10×10) pyramidal needles with a tip-to-tip distance of 500 µm and height of 550 µm. The graphene incorporation reinforced the mechanical strength of the microneedles and facilitated their insertion into the skin. Importantly, the graphene/PAA microneedles exhibited good photothermal effects under near-infrared (NIR) irradiation and rapid drug delivery behavior due to the good water solubility of the PAA matrix. Hence, the resulting graphene/PAA microneedles have great potential for application in synergistic chemo- and photothermal therapies for skin cancer.

Metal-organic framework-coated magnetite nanoparticles for synergistic magnetic hyperthermia and chemotherapy with pH-triggered drug release.

In nanoplatform-based tumor treatment, combining chemotherapy with hyperthermia therapy is an interesting strategy to achieve enhanced therapeutic efficacy with low dose of delivery drugs. Compared to photothermal therapy, magnetic hyperthermia has few restrictions on penetrating tissue by an alternating magnetic field, and thereby could cure various solid tumors, even deep-tissue ones. In this work, we proposed to construct magnetic nanocomposites (Fe3O4@PDA@ZIF-90) by the external growth of metal-organic framework ZIF-90 on polydopamine (PDA)-coated Fe3O4 nanoparticles for synergistic magnetic hyperthermia and chemotherapy. In such multifunctional platform, Fe3O4 nanoparticle was utilized as a magnetic heating seed, PDA layer acted as an inducer for the growth of ZIF-90 shell and porous ZIF-90 shell served as drug nanocarrier to load doxorubicin (DOX). The well-defined Fe3O4@PDA@ZIF-90 core-shell nanoparticles were displayed with an average size of ca. 200 nm and possessed the abilities to load high capacity of DOX as well as trigger drug release in a pH-responsive way. Furthermore, the Fe3O4@PDA@ZIF-90 nanoparticles can raise the local temperature to meet hyperthermia condition under an alternating magnetic field owing to the magnetocaloric effect of Fe3O4 cores. In the in vitro experiments, the Fe3O4@PDA@ZIF-90 nanoparticles showed a negligible cytotoxicity to Hela cells. More significantly, after cellular internalization, the DOX-loaded Fe3O4@PDA@ZIF-90 nanoparticles exhibited distinctively synergistic effect to kill tumor cells with higher efficacy compared to chemotherapy or magnetic hyperthermia alone, presenting a great potential for efficient tumor therapy.

Mesoporous Silica Nanoparticles Capped with Graphene Quantum Dots for Potential Chemo-Photothermal Synergistic Cancer Therapy.

In this study, mesoporous silica nanoparticles (MSNs) have been successfully capped with graphene quantum dots (GQDs) to form multifunctional GQD-MSNs with the potential for synergistic chemo-photothermal therapy. The structure, drug-release behavior, photothermal effect, and synergistic therapeutic efficiency of GQD-MSNs to 4T1 breast cancer cells were investigated. The results showed that GQD-MSNs were monodisperse and had a particle size of 50-60 nm. Using doxorubicin hydrochloride (DOX) as a model drug, the DOX-loaded GQD-MSNs (DOX-GQD-MSNs) not only exhibited pH- and temperature-responsive drug-release behavior, but using near-infrared irradiation, they efficiently generated heat to kill cancer cells. Furthermore, GQD-MSNs were biocompatible and were internalized by 4T1 cells. Compared with chemotherapy and photothermal therapy alone, DOX-GQD-MSNs were much more effective in killing the 4T1 cells owing to a synergistic chemo-photothermal effect. Therefore, GQD-MSNs may have promising applications in cancer therapy.

Proton Conductance of a Superior Water-Stable Metal-Organic Framework and Its Composite Membrane with Poly(vinylidene fluoride).

Proton-exchange membranes (PEMs) as separators have important technological applications in electrochemical devices, including fuel cells, electrochemical sensors, electrochemical reactors, and electrochromic displays. The composite membrane of a proton-conducting metal-organic framework (MOF) and an organic polymer combines the unique physical and chemical nature of the polymer and the high proton conductivity of the MOF, bringing together the best of both components to potentially fabricate high-performance PEMs. In this study, we have investigated the proton-transport nature of a zirconium(IV) MOF, MOF-808 (1). This superior-water-stability MOF shows striking proton conductivity with σ = 7.58 × 10-3 S·cm-1 at 315 K and 99% relative humidity. The composite membranes of 1 and poly(vinylidene fluoride) (PVDF) have further been fabricated and are labeled as 1@PVDF-X, where X represents the mass percentage of 1 (as X%) in 1@PVDF-X and X = 10-55%. The composite membranes exhibit good mechanical features and durability for practical application and a considerable proton conductivity of 1.56 × 10-4 S·cm-1 in deionized water at 338 K as well. Thus, the composite membranes show promising applications as alternative PEMs in diverse electrochemical devices.

Both Dielectrics and Conductance Anomalies in an Open-Framework Cobalt Phosphate.

Switchable conducting or dielectric materials, as the key component, show important technological applications in modern electrical and electronic devices, including data communication, phase shifters, varactors, and rewritable optical data storage. To explore new types of switchable conducting or dielectric materials could significantly accelerate the development of efficient electrical and electronic devices. Herein we present the first example of switchable conducting and dielectric material, which is based on an open-framework phosphate, (C2N2H10)0.5CoPO4. A reversible isostructural phase transition occurs at ∼348 K in this open-framework phosphate, to give both dielectrics and conductance anomaly around the critical temperature of phase transition. This study will provide a roadmap for searching new switchable conducting or dielectric materials as well as new applications of open-framework phosphates.

Crystal structure of bis-[1-(4-bromo-benz-yl)pyridinium] bis-(1,2-di-cyano-ethene-1,2-di-thiol-ato-κ(2) S,S')nickelate(II).

The asymmetric unit of the title salt, (C12H11BrN)2[Ni(C4N2S2)2], consists of one 1-(4-bromo-benz-yl)pyridinium cation and one half of a complex [Ni(mnt)2](2-) (mnt(2-) is the maleo-nitrile-dithiol-ate dianion). The Ni(2+) ion is located on an inversion centre and is coordinated by four S atoms from two mnt(2-) ligands, exhibiting a square-planar coordination environment. In the cation, the planes of the pyridinium and benzene rings make a dihedral angle of 69.86 (19)°. The cations and anions are alternately arranged in layers parallel to (001) and are held together by non-classical C-H⋯N hydrogen bonds.

Polymorph transformation in a mixed-stacking nickel-dithiolene complex with the derivative of 4,4'-bipyridinium.

In this study, two polymorphs of the [1,1'-dibutyl-4,4'-bipyridinium][Ni(mnt)2] salt (1) were synthesized. The dark-green polymorph (designated as 1-g) was prepared under ambient conditions by the rapid precipitation method in aqueous solutions. Subsequently, the red polymorph (labeled as 1-r) was obtained by subjecting 1-g to ultrasonication in MeOH at room temperature. Microanalysis, infrared spectroscopy, thermogravimetry (TG), differential scanning calorimetry (DSC), and powder X-ray diffraction (PXRD) techniques were used to characterize the two polymorphs. Both 1-g and 1-r exhibit structural phase transitions: a reversible phase transition at ∼403 K (∼268 K) upon heating and 384 K (∼252 K) upon cooling for 1-g (1-r) within the temperature range below 473 K. Interestingly, on heating 1-r to 523 K, an irreversible phase transition occurred at about 494 K, resulting in the conversion of 1-r into 1-g. Relative to 1-r, 1-g represents a thermodynamically metastable phase wherein numerous high-energy conformations in butyl chains of cations are confined within the lattice owing to quick precipitation or rapid annealing from higher temperatures. Through variable-temperature single crystal and powder X-ray diffractions, UV-visible spectroscopy, dielectric spectroscopy, and DSC analyses, this study delves into the mechanism underlying phase transitions for each polymorph and the manual transformation between 1-g and 1-r as well.

Anthraquinone/activated carbon electrochemical sensor and its application in acetaminophen analysis.

Acetaminophen (AC) can inhibit the synthesis of prostaglandins in the body, and has antipyretic and analgesic effects. In this paper, a two-step microwave impregnation method was used to prepare anthraquinone (AQ)-doped carbon composite, which were applied to the surface modification of glassy carbon electrodes (GCE) for the determination of acetaminophen (AC) using differential pulse voltammetry (DPV). The composites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman and Fourier infrared spectroscopy (FT-IR). The results showed that anthraquinone was successfully modified on the surface of activated carbon. The peak current of AC increased with its concentration in the range of 0.1 µM to 700 µM (R2 = 0.998) and a detection limit of 0.05 µM was obtained with 20%AQ doped carbon electrochemical sensor (20%AQ-C/GCE). Electrochemical Impedance Spectroscopy (EIS) test results indicated that the charge transfer resistance (Rct) of 20%AQ-C/GCE is only the one-fourth of that of bare GCE. The proposed 20%AQ-C/GCE sensor has good stability, reproducibility and selectivity for the detection of AC. The sensor is also suitable for the detection of real samples, indicating its good practicality.

Covalent organic framework: A state-of-the-art review of electrochemical sensing applications.

Covalent organic framework (COF), a kind of porous polymer with crystalline properties, is a periodic porous framework material with precise regulation at atomic level, which can be formed by the orderly connection of pre-designed organic construction units through covalent bonds. Compared with metal-organic frameworks, COFs exhibit unique performance, including tailor-made functions, stronger load ability, structural diversity, ordered porosity, intrinsic stability and excellent adsorption features, are more conducive to the expansion of electrochemical sensing applications and the universality of applications. In addition, COFs can accurately integrate organic structural units with atomic precision into ordered structures, so that the structural diversity and application of COFs can be greatly enriched by designing new construction units and adopting reasonable functional strategies. In this review, we mainly summarized state-of-the-art recent advances of the classification and synthesis strategy of COFs, the design of functionalized COF for electrochemical sensors and COFs-based electrochemical sensing. Then, an overview of the considerable recent advances made in applying outstanding COFs to establish electrochemical sensing platform, including electrochemical sensor based on voltammetry, amperometry, electrochemical impedance spectroscopy, electrochemiluminescence, photoelectrochemical sensor and others. Finally, we discussed the positive outlooks, critical challenges and bright directions of COFs-based electrochemical sensing in the field of disease diagnosis, environmental monitoring, food safety, drug analysis, etc.

A porous cobalt(II)-organic framework exhibiting high room temperature proton conductivity and field-induced slow magnetic relaxation.

A two-dimensional (2D) cobalt(II) metal-organic framework (MOF) constructed by a ditopic organic ligand, formulated as {[Co(Hbic)(H2O)]·4H2O}n (1) (H2bic = 1H-benzimidazole-5-carboxylic acid), was hydrothermally synthesized and structurally characterized. Single-crystal X-ray diffraction shows that the distorted octahedral Co2+ ions, as coordination nodes, are bridged to form 2D honeycomb networks, which are further organized into a 3D supramolecular porous framework through multiple hydrogen bonds and interlayer π-π interactions. Dynamic crystallography experiments reveal the anisotropic thermal expansion behavior of the lattice, suggesting a flexible hydrogen-bonded 3D framework. Interestingly, hydrogen-bonded (H2O)4 tetramers were found to be located in porous channels, yielding 1D proton transport pathways. As a result, the compound exhibited a high room-temperature proton conductivity of 1.6 × 10-4 S cm-1 under a relative humidity of 95% through a Grotthuss mechanism. Magnetic investigations combined with theoretical calculations reveal giant easy-plane magnetic anisotropy of the distorted octahedral Co2+ ions with the experimental and computed D values being 87.1 and 109.3 cm-1, respectively. In addition, the compound exhibits field-induced slow magnetic relaxation behavior at low temperatures with an effective energy barrier of Ueff = 45.2 cm-1. Thus, the observed electrical and magnetic properties indicate a rare proton conducting SIM-MOF. The foregoing results provide a unique bifunctional cobalt(II) framework material and suggest a promising way to achieve magnetic and electrical properties using a supramolecular framework platform.

Thermochromism of rapid responses to temperature changes versus mechanochromism in a Ni-dithiolene complex salt.

A thermochromic or mechanochromic material can switch between at least two stable states in response to changes in temperature or static pressure/strain. In this study, we investigated a Ni-dithiolene dianion salt, 1,1'-diheptyl-4,4'-bipyridinium bis(maleonitriledithiolato)nickelate (1), and found that its cations and anions stack alternately to form a uniform mixed stack. These mixed stacks then combine to form a molecular solid through Coulomb and van der Waals interactions. Upon heating, 1 undergoes a reversible phase transition at around 340/320 K during the first heating/cooling cycle, resulting in rapid thermochromism with a color change from green (stable state) to red (metastable state) within a few seconds. This is the first report of a crystal of bis(maleonitriledithiolato)nickelate(II) salt with green color. Additionally, 1 exhibits irreversible mechanochromism, intense near-IR absorbance, and a dielectric anomaly. The structural phase transition is responsible for these properties, as it induces alterations in the π-orbital overlap between the anion and cation within a mixed stack. The intense near-IR absorbance arises from the ion-pair charge transfer transition from [Ni(mnt)2]2- to 4,4'-bipyridinium.

Supramolecular encapsulation of hexaaquacobalt(II) cations in a hydrogen-bonded framework for slow magnetic relaxation and high proton conduction.

The supramolecular assembly of hexaaquacobalt(II) nitrate and a tetradentate carboxylate ligand resulted in the isolation of a cobalt hydrogen-bonded organic framework (HOF). Variable-temperature X-ray diffraction experiments reveal high thermal stability of the framework sustained by charge-assisted, multiple hydrogen bonding interactions with the co-former. Interestingly, the material shows field-induced slow relaxation of magnetization originating from the magnetically anisotropic Co2+ ions within the supramolecular framework, revealing a rare single-ion magnet (SIM) HOF. Additionally, the HOF also exhibits high proton conductivity above 100 °C due to the extensive H-bond networks and high content of water and carboxylate within the material. More importantly, these results not only observe the magnetic and electrical properties of an old molecule but also demonstrate a significant turn-on effect of multifunctionalities from non-functional synthons achieved in a supramolecular approach.

Tuning the structure and magnetic properties via distinct pyridine derivatives in cobalt(II) coordination polymers.

Precise modulation of the structure and magnetic properties of coordination compounds is of great importance in the development of framework magnetic materials. Herein, we report that the coordination self-assembly of a neutral cobalt(II) magnetic building block and selective pyridine derivatives as organic linkers has led to two distinct cobalt(II) coordination polymers, {Co(DClQ)2(bpy)}n (1) and {Co2(DClQ)4(tpb)}n (2) (DClQ = (5,7-dichloro-8-hydroxyquinoline; bpy = 4, 4'-dipyridine; tpb = 1,2,4,5-tetra(4-pyridyl)benzene)). Structural analyses revealed that 1 and 2 are one-dimensional (1D) and 2D coordination polymers containing the same neutral magnetic building block [Co(DClQ)2] bridged by bitopic bpy and tetratopic tpb ligands, respectively. Both the complexes have a distorted octahedral CoN4O2 coordination geometry around each cobalt center offered by the bidentate ligand and organic linkers. Magnetic studies reveal large easy-plane and easy-axis magnetic anisotropy for 1 and 2, respectively. However, because of the weak antiferromagnetic coupling between the bpy-bridged CoII centers, no slow relaxation of the magnetization was observed in 1 under both zero or applied dc fields. Interestingly, complex 2 exhibits slow magnetic relaxation under external fields, indicative of a framework single-ion magnet of 2. Theoretical calculations further support the experimental results and unveil that the D values are +65.3 and -91.2 cm-1 for 1 and 2, respectively, while the magnetic exchange interaction was precisely estimated as -0.16 (1) and -0.009 (2) cm-1. The foregoing results show that the structural dimensionality and magnetic properties can be rationally modified via pre-designed magnetic building blocks and a suitable choice of organic bridging ligands.

Field-induced slow magnetic relaxation behaviours in binuclear cobalt(II) metallocycles and exchange-coupled clusters.

Precise control of the structures and magnetic properties of a molecular material constitutes an important challenge to realize tailor-made magnetic function. Herein, we report that the ligand-directed coordination self-assembly of a dianionic cobalt(II) mononuclear complex and selective organic linkers has led to two distinct dicobalt(II) complexes, [Co2(pdms)2(bpym)3]·2MeCN (1) and [Co(pdms)(bipm)]2·3DMF (2) (H2pdms = 1,2-bis(methanesulfonamide)benzene; bpym = 2,2'-bipyrimidine; bimp = 1,4-bis[(1H-imidazol-1-yl)methyl]benzene). Structural analyses revealed that complexes 1 and 2 are discrete binuclear molecules containing two neutral {Co(pdms)} species bridged by bpym and bimp ligands, respectively, forming an exchange-coupled CoII2 dimer and a rare CoII2 metallocycle. Magnetic studies found that 1 exhibits considerable antiferromagnetic interactions transferred by the bpym bridge while negligible magnetic interactions in 2 due to the long bimp ligands. Interestingly, both the complexes show significant magnetic anisotropy and thus exhibit slow magnetic relaxation under an external dc field originating from spin-lattice relaxation. Detailed theoretical calculations were further applied to understand the magnetic interactions and magnetic anisotropy in 1 and 2. The foregoing results highlight that coordination solids with programmed structures and magnetic properties can be designed and prepared through a judicious selection of molecular complex building blocks and organic linkers.

Heterometallic Dual-Liganded AE-Ln-CPs Luminescent Probes for Efficient Sensing of Fe(III) Ions.

Iron ion is widely present in the environment and in biological systems, and are indispensable trace elements in living organisms, so development of an efficient and simple sensor for sensing Fe(III) ions has attracted much attention. Here, six heterometallic AE-Ln coordination polymers (CPs) [Ln2 (pda)4(Hnda)2Ca2(H2O)2]·MeOH (Ln = Eu (1), Tb (2); H2pda = 2,6-pyridinedicarboxylic acid, H2nda = 2,3-naphthalenedicarboxylic acid), [Ln (pda)2 (nda)AE2(HCOO)(H2O)] (AE = Sr, Ln = Eu (3), Tb (4); AE = Ba, Ln = Eu (5), Tb (6)) with two-dimensional (2D) layer structures were synthesized by hydrothermal method. All of them were characterized by elemental analysis, XRD, IR, TG, as well as single crystal X-ray diffraction. They all show infinite 2D network structure, where complexes 1 and 2 are triclinic with space group of P 1 ¯ , while 3-6 belong to the monoclinic system, space group P21/n . The solid-state fluorescence lifetimes of complexes 1, 3 and 5 are τobs1 = 1930.94, 2049.48 and 2,413.04 µs, respectively, and the quantum yields Ф total are 63.01, 60.61, 87.39%, respectively, which are higher than those of complexes 2, 4 and 6. Complexes 1-6 all exhibited efficient fluorescence quenching response to Fe3+ ions in water, and were not interfered by the following metal ions: Cu2+, Cd2+, Mg2+, Ni2+, Co2+, Ca2+, Ba2+, Sr2+, Li+, Na+, K+, Al3+, Fe2+, Pb2+, Cr3+, Mn2+ and Zn2+. The quenching coefficient K SV for complexes 1-6 is 1.41 × 105 M-1, 7.10 × 104 M-1, 1.70 × 105 M-1, 1.57 × 105 M-1, 9.37 × 104 M-1, 1.27 × 105 M-1, respectively. The fluorescence quenching mechanism of these complexes towards Fe3+ ions was also investigated. It is possible that the weak interaction formed between the complexes and the Fe3+ ions reduce the energy transfer from the ligand to the Ln3+ ion, producing the emission burst effect. This suggests that complexes 1-6 can be candidate for efficient luminescent sensor of Fe3+.

A Proton Conducting Cobalt(II) Spin Crossover Complex.

Spin crossover (SCO) complexes have been extensively explored as bistable materials and recently used as molecular modules for the development of new multifunctional molecular magnetic materials. Herein, we present the synthesis, crystal structure, magnetic, and electrical properties of a mononuclear cobalt complex constructed by a halogen-functionalized terpyridine derivative and organosulfonate. A complete and gradual spin transition with the T1/2 =200 K was observed for the Co2+ ions through both the magnetic measurement and dynamic crystallographic experiments. Interestingly, considerable room temperature proton conductivity of 6.9×10-5  S cm-1 under 98% relative humidity was evidenced because of the presence of sulfonate-assisted hydrogen-bonded proton hopping pathways. The forgoing results not only provide an unprecedented proton-conducting cobalt(II) SCO complex but also a promising way for the design and construction of bifunctional SCO molecular conductors via the incorporation of SCO transition and proton conduction.

A single-ion magnet building block strategy toward Dy2 single-molecule magnets with enhanced magnetic performance.

A molecular dysprosium(III) complex [Dy(DClQ)3(H2O)2] (1) was used as a building unit for the construction of lanthanide SMMs, leading to the isolation of two dinuclear Dy(III) complexes, namely [Dy2(DClQ)6(MeOH)2] (2) and [Dy2(DClQ)6(bpmo)2]·6MeCN (3) (DClQ = 5,7-dichloro-8-hydroxyquinoline, bpmo = 4,4'-dipyridine-oxide). Structural analyses revealed the same N3O5 coordination environment of the Dy(III) centers with a distorted biaugmented trigonal prism (C2V symmetry) and triangular dodecahedron (D2d symmetry) for 2 and 3, respectively. Magnetic studies revealed the presence of ferromagnetic and weak antiferromagnetic exchange interactions between the Dy3+ centers in 2 and 3, respectively. Interestingly, slow relaxation of magnetization at zero fields was evidenced with an Ueff of 51.4 K and 159.0 K for complexes 2 and 3, respectively. The detailed analysis of relaxation dynamics discloses that the Orbach process is dominant for 2 whereas Raman and QTM play an important role in 3. Theoretical calculations were carried out to provide insight into the magnetic exchange interactions and relaxation dynamics for the complexes. Due to a single-ion magnet (SIM) of 1, the foregoing results demonstrate a SIM modular synthetic route for the preparation of dinuclear lanthanide SMMs.

Stack pattern of the countercation-modulating magnetic property of low-dimensional [Pt(mnt)2]⁻ monoanion spin systems.

Three [1-N-(4'-R-benzyl)-4-aminopyridinium][Pt(mnt)(2)] compounds were structurally and magnetically characterized, where the substituent was attached to the para-position of the phenyl ring (R = CN (1), Cl (2), and H (3); mnt(2-) = maleonitriledithiolate). 1 and 2 crystallized in the monoclinic space group P2(1)/c, with the cations and anions forming segregated columnar stacks. Their structural differences involved two aspects: (1) both anion and cation stacks were regular in 1 and irregular in 2; (2) the neighboring cations were arranged in the boat-type pattern in 1, whereas these cations were in the chair-type pattern in 2 within the cation stack. 3 belonged to the triclinic space group P ̅1, where the anions were assembled into the stack with a tetrameric [Pt(mnt)(2)](-) subunit, but the cations did not form the columnar stack. Magnetic measurements disclosed that a spin-Peierls-type transition occurred around 240 K for 1, whereas a long-range, antiferromagnetic ordering took place at about 5.8 K, and a metamagnetic phenomenon was observed with H(C) ≈ 1000 Oe for 2; 3 showed very strong antiferromagnetic interactions with diamagnetism in the temperature range 5-300 K. Combined with our previous studies, the correlation between the stacking pattern of benzylpyridinium derivatives in a cation stack and the spin-Peierls-type transition is discussed for the series of quasi-1-D [M(mnt)(2)](-) (M = Ni, Pd and Pt) compounds.