An octacoordinated Fe(II) complex, [FeII(dpphen)2](BF4)2·1.3H2O (1; dpphen = 2,9-bis(pyrazol-1-yl)-1,10-phenanthroline), with a pseudo-D2d-symmetric metal center has been synthesized. Magnetic, high-frequency/-field electron paramagnetic resonance (HF-EPR), and theoretical investigations reveal that 1 is characterized by uniaxial magnetic anisotropy with a negative axial zero-field splitting (ZFS) (D ≈ −6.0 cm–1) and a very small rhombic ZFS (E ≈ 0.04 cm–1). Under applied dc magnetic fields, complex 1 exhibits slow magnetic relaxation at low temperature. Fitting the relaxation time with the Arrhenius mode combining Orbach and tunneling terms affords a good fit to all the data and yields an effective energy barrier (17.0 cm–1) close to the energy gap between the ground state and the first excited state. The origin of the strong uniaxial magnetic anisotropy for 1 has been clearly understood from theoretical calculations. Our study suggests that high-coordinated compounds featuring a D2d-symmetric metal center are promising candidates for mononuclear single-molecule magnets.

•Four short axially symmetrically (4a, 4b) and asymmetrically (4c, 4d) substituted pyrenes were synthesized.•The structures of 4a and 4b were determined by single-crystal X-ray diffraction analysis.•The four compounds exhibit high absolute ΦFs in dichloromethane (83.31–88.45%).•Electroluminescent devices using 4a and 4b as doped emission layer were fabricated.A new series of short axially symmetrically (4a and 4b) and asymmetrically (4c and 4d) 1,3,6,8-tetrasubstituted pyrene-based compounds with two phenyl moieties and two diphenylamine units on the pyrene core were designed and synthesized based on stepwise synthetic strategy. These compounds were structurally characterized and their photoelectric properties were investigated by spectroscopy, electrochemical and theoretical studies. The structures of 4a and 4b were determined by single-crystal X-ray diffraction analysis, indicating that the compounds are twisted by the peripheral substituents and the intermolecular π-π interactions have been efficiently interrupted. The four compounds exhibit high absolute fluorescence quantum yields (ФF) in dichloromethane (83.31–88.45%) and moderate ФFs in film states (20.78–38.68%). In addition, compounds 4a and 4b display relatively higher absolute ФFs than those of 4c and 4d in film states. All the compounds exhibit high thermal stability with decomposition temperatures above 358 °C and the values of 4c and 4d are higher than 4a and 4b. Compounds 4a and 4b can form morphologically stable amorphous thin films with Tg values of 146 °C and 149 °C, respectively. However, there are no obvious Tg observed in compounds 4c and 4d. Electroluminescent devices using 4a and 4b as doped emission layer show promising device performance with low turn-on voltage (3.0 V), maximum brightness around 15100 cd/m2 and 16100 cd/m2, maximum luminance efficiency of 12.4 cd/A and 13.6 cd/A and maximum external quantum efficiency of 5.34% and 5.63%, respectively.A new series of short axially symmetrically and asymmetrically 1,3,6,8-tetrasubstituted pyrenes with two types of substituents were designed and synthesized. Electroluminescent devices using the compounds 4a and 4b as doped emission layer show promising device performance.

A cyanide-bridged CrI–CoII heterometallic complex {[CoII(LN5)]3[CrI(CN)5(NO)]2·CH3CN·3H2O]}n (LN5 = 2,13-dimethyl-3,6,9,12,18-pentaazabicyclo[12.3.1]octadeca-1(18),2,12,14,16-pentaene) has been synthesized based on [CoII(LN5)2(H2O)2]·(ClO4)2 and the pentacyanide building block K3[CrI(CN)5(NO)]. Single-crystal X-ray diffraction analysis shows that the complex is a cyanide-bridged two-dimensional Cr2ICo3II complex, linked together by hydrogen bonds to form a three-dimensional network. Magnetic investigations show that the magnetic coupling between the Cr(I) and Co(II) centers through the cyanide bridges is ferromagnetic. The complex displays typical soft ferromagnet behavior with a three-dimensional ferromagnetic ordering and Tc = 3.5 K.

•The probe displays unique two fluorescence emissions due to the tautomerization through the ESIPT process.•The probe detected Zn2+ ion through ESIPT and CHEF processes.•The probe was capable of concurrently high sensitive and selective detecting Zn2+ ion.A new tetraphenylethene-based fluorescent probe 2-(quinolin-8-yliminomethyl)-4-triphenylvinyl-phenol (HL) for detecting Zn2+ ion through the excited state intramolecular proton transfer (ESIPT) and chelation enhanced fluorescence (CHEF) processes has been designed and synthesized. The results show that HL emits relatively strong blue fluorescence at 460 nm without Zn2+ ion, however, probe HL displays highly pink fluorescent emission at 600 nm when adding Zn2+ ion. The fluorescent emission of HL appears an extremely large Stokes shift, which effectively reduces the interference of background signal. The limit of detection of HL for Zn2+ ion can reach to 9.0 × 10–8 M.A new tetraphenylethene-based Schiff base HL was designed and synthesized. Compound HL shows high sensitivity and excellent selectivity for Zn2+ ion as a fluorescent probe.Download high-res image (74KB)Download full-size image

•Pyrene-based fluorophore as a novel fluorescent dye for developing a fluorescent probe Py-Boe with large Stokes shift in various solutions.•The probe Py-Boe is capable of concurrently high sensitive and selective detecting H2O2 in aqueous solution.•The probe Py-Boe is capable of detecting exogenous and endogenous H2O2 in mitochondria of living RAW 264.7 cellsHydrogen peroxide (H2O2) plays an important role in signal transduction and therapy of serious diseases. In this work, we have developed a new pyrene-based fluorescent probe Py-Boe, which possesses large Stokes shift and achieves detection of H2O2 in aqueous solution. The probe Py-Boe exhibits excellent photostability, high sensitive and selectivity. Taking advantage of these properties, the probe Py-Boe achieves succussfully imaging of exogenous and endogenous H2O2 in living RAW 264.7 cells. We expect that this dye with large Stokes shift may open an avenue to construct novel fluorescent probe with large Stokes shift for biological application.Herein, we have developed a new pyrene-based fluorescent probe Py-Boe with large Stokes shift and achieved high sensitive detection of H2O2 in aqueous solution. Furthermore, the probe Py-Boe is suitable for detecting exogenous and endogenous H2O2 in living RAW 264.7 cells.Download high-res image (131KB)Download full-size image

It is important to develop fluorescent probes for rapid, selective, and sensitive detection of highly toxic hydrazine in both environmental and biological science. In this text, under mild conditions, a novel near-infrared (NIR) ratiometric and on–off fluorescent probe 1 was synthesized based on hemicyanine and coumarin derivatives, which can detect hydrazine with high selectivity and anti-interference over other amines, biological species, anions and metal ions. The limit of quantification (LOQ) value was 0–400 μM and the detection limit could be as low as 560 nM.

A new tetraphenylethene-based Schiff base N-5-nitrosalicylidene-4-tetraphenylethenylamine (NSTPE) was synthesized based on 4-tetraphenylethenylamine and 5-nitrosalicylaldehyde, and its structure was fully characterized by 1H NMR, 13C NMR, MS and single crystal X-ray diffraction analysis. The study of optical properties shows that the emission exhibits an interesting “on–off–on” switching property with a U-shaped tendency when adding water into the tetrahydrofuran solution of NSTPE, showing twisted intramolecular charge transfer (TICT) and aggregation-induced emission (AIE) characteristics. Moreover, the compound exhibits reversible piezofluorochromic properties.

Five dipyrenyl-based triarylamines N-p-(R)-phenyl-N,N-dipyrenyl-1-amine (R = H (2a), CH3 (2b), OCH3 (2c), F (2d), NO2 (2e)) and one tripyrenyl-based triarylamine N,N-bis(7-tert-butylpyren-1-yl)-N-pyrenyl-1-amine (3py) were successfully synthesized by copper- and palladium-catalyzed coupling reactions in high yields. These compounds were structurally characterized and their photoelectric properties were analyzed by spectroscopy, electrochemical and theoretical studies. Moreover, the structures of 2b, 2c and 2d were determined by single-crystal X-ray diffraction analysis, indicating that the three compounds are all twisted paddle-like structures with a nitrogen atom as the linking center and the substituent attached to the para position of the benzene ring has an important effect on the intermolecular interactions. Compounds 2a–2d and 3py show green fluorescence emissions with excellent absolute fluorescence quantum yields in toluene (66.06–86.06%). Compound 2e displays a faint emission with a very low quantum yield because of the effect of the strong electron-withdrawing nitro group. They are thermally stable with decomposition temperatures above 355 °C. Organic light-emitting diodes incorporating the materials 2c and 2d as non-doped emitters were fabricated.

To promote the practical application of novel heteroatom-doped carbon electrocatalysts for the oxygen reduction reaction (ORR) in fuel cells, in this work, low-cost nitrogen (N), sulfur (S) and phosphorus (P)-ternary doped carbon nano-pore/tube composites (NSP-CNPTCs) were synthesized by natural, cheap and environment-friendly N, S and P-containing chemicals extracted from waste sweet osmanthus fruit and a certain amount of dicyandiamide with ferric sulfate as a catalyst. Electrochemical tests demonstrated that the as-prepared NSP-CNPTCs exhibited superior ORR activity in both acidic and alkaline media, showing a new approach for utilizing natural heteroatom-containing chemicals in all heteroatom-rich biomasses to synthesize value-added heteroatom-doped carbon electrocatalysts in future fuel cells.

Four tetraphenylethene-based benzimidazoles 5,6-R-2-(4-tetraphenyletheneyl)-1H-benzo[d]imidazoles (R = H (2a), Cl (2b), Br (2c) and CH3 (2d)) were conveniently synthesized in high yields by the cyclization reaction of 4-tetraphenylenthenealdehyde with phenylenediamines. These compounds were structurally characterized and their properties were analyzed by spectroscopy, electrochemistry, X-ray diffraction, thermal stability and theoretical studies. Single crystal X-ray diffraction analyses indicate that their molecular structures in the aggregated state are highly twisted conformations and there exist obvious cavities and/or interface gaps in their crystal packing structures. These four compounds exhibit typical aggregation-induced emission (AIE) properties with relatively high absolute fluorescence quantum yields (30.6–67.5%). These compounds also exhibit reversible mechanochromism behaviors with emission changes between light blue and yellow-green, which are due to the reversible morphological transformation between unconsolidated crystalline state and amorphous state. They are thermally stable with decomposition temperatures above 340 °C.

Correction for ‘A new series of pyrenyl-based triarylamines: syntheses, structures, optical properties, electrochemistry and electroluminescence’ by Ran Zhang et al., RSC Adv., 2016, 6, 9037–9048.

•Two new enlarged tetraarylethene-based compounds have been synthesized by a convenient method.•Both the compounds exhibit aggregation-induced emission characteristics.•Both the compounds have good thermal stability and high emission efficiency in solid state.•Relationship between aggregation morphology and emission efficiency have been revealed.Two new enlarged tetraarylethene-based compounds in which biphenyl and 4,5,9,10-tetrahydropyrene cores connect multiple arylethene units have been synthesized through convenient synthetic procedures. The optical properties and electrochemical properties of the two compounds have been investigated. The two compounds possess high emission efficiency in solid state. Particularly, the absolute fluorescence quantum yield of 4,5,9,10-tetrahydropyrene-cored compound in a solid film is up to 44.1%. The emissions of the two compounds in solutions are very weak but they become strong emitters in solid state or in poor solvents, showing aggregation-induced emission (AIE) characteristics. The two compounds exhibit high thermal stability with Td above 427 °C and show relatively high glass transition temperature with Tg above 142 °C.Two new tetraarylethene-based compounds with enlarged π-conjugation have been synthesized by a convenient method. These two compounds show aggregation-induced emission properties and have application potential in organic electroluminescence devices.

•The first cyanide-bridged two-dimensional CrIIICoII complex has been synthesized.•The complex displays typical ferromagnet behaviors with Tc = 15.0 K.A new cyanide-bridged CrIIICoII heterometallic complex {[Co(L-N5)]3[Cr(CN)6]2}n·nCH3CN·5nH2O (1) has been synthesized by the reaction of [CoII(L-N5)2(H2O)2]·(ClO4)2 with the hexacyanidechromate(III) building block K3[CrIII(CN)6]. X-ray single crystal diffraction analysis shows that complex 1 has a two-dimensional (2D) layer-like structure. Magnetic investigations show that the magnetic coupling between Cr(III) and Co(II) ions through cyanide bridge is ferromagnetic for the complex. The complex displays typical soft ferromagnet behaviors with a three-dimensional ferromagnetic ordering of Tc = 15.0 K, a small coercive field of 10 Oe and a remnant magnetization of about 7.8 Nβ.A new cyanide-bridged two-dimensional CrIIICoII complex has been synthesized. Magnetic property investigations show that the complex is a typical ferromagnetic with Tc = 15.0 K.

•Six new CrIII–MnIII 1D neutral complexes have been designed and synthesized.•These complexes show weak antiferromagnetic coupling.•The magnetic properties are fitted based on the suitable 1D CrIII–MnIII magnetic model.•The magneto-structural correlation for CrIII–MnIII complexes has been discussed.Six new cyanide-bridged CrIII–MnIII one-dimensional (1D) complexes [MnIII(salen)CrIII(bpb)(CN)2]n (1), [MnIII(5-Clsalen)CrIII(bpb)(CN)2·0.5CH3OH·H2O]n (2), [MnIII(5-Brsalen)CrIII(bpb)(CN)2·0.5CH3OH·H2O]n (3), [MnIII(5-MeOsalen)CrIII(bpb)(CN)2·H2O]n (4), [MnIII(5-Clsalen)CrIII(bpClb)(CN)2·CH3CN]n (5) and [MnIII(5-Brsalen)CrIII(bpClb)(CN)2·2H2O]n (6) have been rationally designed, controlling synthesized and structurally characterized based on [MnIII(5-R1salen)]+ and [CrIII(4-R2bpb)(CN)2]− building blocks [5-R1salen2− = N,N′-ethylenebis(5-R1-salicylideneaminato)dianion, R1 = H for salen2−, Cl for 5-Clsalen2−, Br for 5-Brsalen2− and MeO for 5-MeOsalen2−; 4-R2bpb2− = 1,2-bis(pyridine-2-carboxamido)-4-R2-benzenate, R2 = H for bpb2− and Cl for bpClb2−]. The single crystal structures of these complexes consist of alternating units of [MnIII(5-R1salen)]+ and [CrIII(4-R2bpb)(CN)2]−, forming cyanide-bridged neutral 1D complexes. Investigation over magnetic properties of these complexes reveals the whole relatively weak antiferromagnetic interactions between Mn(III) ion and Cr(III) through cyanide bridge. The magnetic susceptibilities of these complexes were fitted based on the suitable 1D CrIII–MnIII magnetic model. The magneto-structural correlation for cyanide-bridged CrIII–MnIII systems reveals that the cyanide-bridging bond angle is related to the magnitude of magnetic exchange coupling: the larger the MnNC bond angle, the weaker antiferromagnetic interactions.Six new cyanide-bridged CrIII–MnIII 1D complexes have been synthesized and structurally characterized. These complexes all exhibit overall weak antiferromagnetic interactions. The magnetic susceptibilities of these complexes were fitted based on the suitable 1D CrIII–MnIII magnetic model. The magneto-structural correlation for CrIII–MnIII complexes have been discussed.

•A novel rhodamine and 8-hydroxyquinoline-based chemosensor for Fe3 + has been developed.•The probe can quantitatively detect Fe3 + with a distinct color change from colorless to pink within 1 min.•The ‘in situ’ prepared complex showed high selectivity and sensitivity (the LOD can be as low as 71 nM) toward PPi.A novel rhodamine and 8-hydroxyquinoline-based derivative was synthesized, which is shown to act as a colorimetric chemosensor for Fe3 + in aqueous solution with high selectivity over various environmentally and biologically relevant metal ions and anions with a distinct color change from colorless to pink in very fast response time (< 1 min). Fe3 + can be detected quantitatively in the concentration range from 6.7 to 16 μM and the detection limit (LOD) on UV–vis response of the sensor can be as low as 15 nM. The ‘in situ’ prepared Fe3 + complex (1 ⋅ Fe) showed high selectivity toward PPi against many common anions, and sensitivity (the LOD can be as low as 71 nM). In addition, both the chemosensor and the ‘in situ’ prepared Fe3 + complex are reusable for the detection of Fe3 + and PPi respectively.A novel rhodamine and 8-hydroxyquinoline-based chemosensor and the ‘in situ’ prepared Fe3 + complex are reusable for the detection of Fe3 + and PPi respectively.

•A new series of tetra(polycyclic aryl)ethenes have been synthesized.•A convenient method to prepare the di(polycyclic aryl) ketone have been developed.•All of the three luminogens exhibit aggregation-induced emission characteristics.•A new strategy to obtain efficient solid-state emitter has been proposed.Three novel ethene derivatives substituted by four polycyclic aromatic hydrocarbons, tetrakis(4,5,9,10-tetrahydropyren-2-yl)ethene, tetra(fluoren-2-yl)ethene and tetra(biphenyl-4-yl)ethene, were efficiently synthesized and characterized by NMR spectroscopy, mass spectrometry and elemental analysis. The optical properties, electrochemical properties of the three compounds have been investigated and contrasted with results from theoretical calculations. These luminogens are weakly fluorescent in solutions, but are highly emissive in the condensed phase, revealing distinct aggregation-induced emission characteristics. The fluorescence quantum yield of tetrakis(4,5,9,10-tetrahydropyren-2-yl)ethene in a solid film is up to 74.1%, which is much higher than that of the two others. The electronic structures and energy levels were calculated using the B3LYP/6-31G(d) basis set. A crystal structure study indicates that there are no π-stacking interactions formed between tetrakis(4,5,9,10-tetrahydropyren-2-yl)ethene molecules in the crystal phase. This study reveals that when constructing aggregation-induced emission molecules using substituent groups with expanded π-conjugation, introduction of appropriate steric hindrance on the substituent groups can restrict the formation of excimers effectively, hence achieving efficient solid state emission.Adopting 4,5,9,10-tetrahydropyrene with expanded π-conjugation as well as certain steric hindrance to construct tetrakis(4,5,9,10-tetrahydropyren-2-yl)ethene can restrict the formation of π–π interactions. This is an effective strategy to obtain luminogens showing both aggregation-induced emission and efficient solid-state photoluminescence.

•A linear-chain cobalt coordination polymer has been synthesized.•The complex is a chiral polymer assemblied from achiral components.•The complex undergoes valence tautomeric interconversion.A linear-chain cobalt coordination polymer, [Co(2,3-LH2)2(4,4′-bipy)]⋅2H2O⋅4,4′-bipy]n (1) (2,3-LH2 = 2,3-tetrahydroxy-9,10-dimethyl-9,10-dihydro- 9,10-ethanoanthracene, 4,4′-bipy = 4,4′-bipyridine), has been synthesized and structurally characterized. Single-crystal X-ray analysis reveals that complex 1 is a chiral polymer assemblied from achiral components. The complex 1 crystallizes in the chiral space group P3221 and the central Co ion has a slightly distorted octahedral coordination environment. The temperature dependence of magnetic susceptibility indicates that the complex 1 undergoes valence tautomeric interconversion between low-spin ls-[CoIII(2,3-LH2Cat)(2,3-LH2SQ)] and high-spin hs-[CoII(2,3-LH2SQ)2] (2,3-LH2Cat = 2,3-LH2catecholate, 2,3-LH2SQ = 2,3-LH2semiquinone).

•Cu2O crystals with average sizes ranging from 25 to 282 nm were synthesized.•Concentration of PVP and acid ions has great influences on the final morphologies.•Morphologies were less dependent on the concentration of NO3− compared with Ac−.•Self-assembly of Cu2O crystals was observed through a route of 0D → 2D → 3D.•Cu2O nanospheres exhibit better adsorption ability toward MO than AC does.Cu2O crystals with different morphologies (solid and porous) and sizes (from 25 to 282 nm) were synthesized controllably through a facile solvothermal route. The growth mechanism was investigated by SEM and TEM with varying the concentration of poly (vinylpyrrolidone) (PVP, K30), CH3COO− (Ac−) and NO3− acid ions in the precursor solution. The self-assembly of three types of Cu2O nano-structures was observed through a general route of zero-dimensional (0D) → 2D → 3D. When Cu(Ac)2⋅H2O was used as the copper sources, 0D Cu2O nanodots with size of 2–7 nm were firstly assembled to 2D quasi-spherical and bookmark-like structures via Oriented attachment (OA), and then converted into 3D hierarchical Cu2O nanoclusters (a few tens of nm) and porous sub-microspheres with an average size of 282 nm, respectively. While Cu(NO3)2⋅3H2O was used instead of Cu(Ac)2⋅H2O, the similar assembly process occurred leading to the formation of Cu2O porous nanospheres of 40–140 nm which exhibit better adsorption ability toward methyl orange compared with activated carbon. In addition, we also investigated the dependence of Cu2O crystals on the concentration of acid ions (Ac− and NO3−). Compared with Ac−, the size and morphology of the obtained products were less dependent on the concentration of NO3− acid ions. This study might provide a new insight into the growth mechanism of Cu2O based micro- or nanostructures.The growth mechanism of porous Cu2O nanospheres was revealed successfully, which involved a self-assembly process from nanodots (0D) to nanosheets (2D) and nanospheres (3D).

Two cyanato-bridged dinuclear Mn(II) complexes [Mn2(phen)4(μ1,1-NCO)2][MIII(bpb)(CN)2]·H2O [M = Fe (1) or Co (2)], [phen = 1,10-phenanthroline, bpb2− = 1,2-bis(pyridine-2-carboxamido)benzenate] have been synthesized using the synthetic strategy of big anion inducement. Single-crystal X-ray diffraction analysis reveals that both complexes consist of a double end-on (EO) cyanato-bridged dinuclear Mn(II) unit and two free [M(bpb)(CN)2]− building blocks acting as counter-ions. Magnetic studies show the presence of abnormal antiferromagnetic interactions between the two Mn(II) centers through the EO cyanate bridge with J = −1.58(3) cm−1 for complex 1 and −1.82(2) cm−1 for complex 2. The unusual antiferromagnetic interactions of these complexes can be attributed to their small Mn(II)–N–Mn(II) angles.

Four heterobimetallic trinuclear FeШ–CuII–FeШ complexes [Cu(cyclam)][Fe(bpb)(CN)2]2·4H2O (1), [Cu(cyclam)][Fe(bpClb)(CN)2]2·4H2O (2), [Cu(cyclam)][Fe(bpmb)(CN)2]2·4H2O (3) and [Cu(cyclam)][Fe(bpdmb)- (CN)2]2·H2O (4) (cyclam = 1,4,8,11-tetraazacyclotetradecane, bpb2– = 1,2-bis(pyridine-2-carboxamido), bpClb2− = 1,2-bis(pyridine-2-carboxamido)-4-chloro-benzenate, bpmb2− = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate, bpdmb2– = 1,2-bis(pyridine-2-carboxamido)-4,5-dimethyl-benzenate) have been synthesized based on cyanide-containing building blocks [Fe(L)CN2]− (L = bpb2−, bpClb2−, bpmb2− and bpdmb2−) and [Cu(cyclam)]2+. Their structures and magnetic properties were investigated. The single-crystal X-ray diffraction analyses reveal that they are all neutral trinuclear sandwich-like structures. Magnetic investigations show that they are all abnormal antiferromagnetic, with J = −0.95 cm−1 for 1, −0.70 cm−1 for 2, −0.93 cm−1 for 3 and −0.85 cm−1 for 4 based on the Hamiltonian Ĥ = −2 JŜCu(ŜFe(1) + ŜFe(2)). The abnormal antiferromagnetic coupling between Fe(III) and Cu(II) in the four complexes can be attributed to the small Cu–N≡C bond angles.

1-Thiohydroxypyrene(1) and its two intermediates, 1-pyrenyl-O-thiocarbamate(2) and 1-pyrenyl-S-thiocarbamate(3), were synthesized using 1-hydroxypyrene as the starting material. The key synthetic step is Newman-Kwart rearrangement. The results indicate that the Newman-Kwart rearrangement is more effective in suitable solvent than conventional method based on pure organic compound. The structures of compounds 1–3 were characterized by FTIR, NMR, GC-MS and elementary analysis. The crystal structures of two new compounds(2 and 3) were determined by single crystal X-ray diffraction analysis. The whole synthetic process is simple, mild and with high yield.

Four azido-bridged dinuclear Mn(II) complexes, [Mn2(phen)4μ-1,1-N3)2][FeIII(bpmb)(CN)2]2·H2O (1), [Mn2(phen)4(μ-1,1-N3)2][FeIII(bpClb)(CN)2]2·H2O (2), and [Mn2(phen)4(μ-1,1-N3)2][MIII(bpdmb)(CN)2]2·3H2O [M = Fe (3) or Cr (4); phen = 1,10-phenanthroline, bpmb2– = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate, bpClb2– = 1,2-bis(pyridine-2-carboxamido) 4-chloro-benzenate, bpdmb2– = 1,2-bis(pyridine-2-carboxamido)-4,5-dimethyl-benzenate], have been synthesized using the synthetic strategy of large anion inducement. Single-crystal X-ray diffraction analysis reveals that all four complexes are doubly end-on (EO) azido-bridged binuclear Mn(II) complexes with two large [M(L)(CN)2]– (L = bpmb2−, bpClb2−, or bpdmb2−) building blocks acting as charge-compensating anions. The magnetic properties of the complexes have been investigated, and the results indicate that the magnetic coupling between two Mn(II) centers through the EO azide bridges is ferromagnetic, with J = 0.64(1) cm−1 for 1, 0.43(1) cm−1 for 2, 0.50(1) cm−1 for 3, and 0.66(2) cm−1 for 4. The magneto-structural relationships of EO azido-bridged Mn(II) systems are discussed.

•A new cyanide-bridged 2D complex has been synthesized.•The complex shows intralayer ferromagnetic coupling and a magnetic ordering.•The typical metamagnetic behaviors were observed in this complex.A cyanide-bridged FeIII–CoII heterometallic complex {[Fe(1-CH3im)(CN)5][Co(H2O)2]}n·3H2O (1-CH3im = 1-methylimadazole) (2) has been synthesized by the reaction of CoII(ClO4)2·6H2O with the pentacyanideferrite(III) building block (Ph4P)2[FeIII(1-CH3im)(CN)5]·4.5H2O (1). X-Ray single crystal diffraction analysis shows that complex 2 has a two-dimensional (2D) grid-like structure. Magnetic investigations show that complex 2 displays long-range antiferromagnetic ordering with TN = 9.45 K. The typical metamagnetic behaviors were observed with the critical field of ca. 4000 Oe at 1.82 K.A new cyanide-bridged two-dimensional grid-like binuclear FeIII–CoII complex {[Fe(1-CH3im)(CN)5]-[Co(H2O)2]}n·3H2O (1-CH3im = 1-methylimadazole) (2) based on the pentacyanideferrite(III) building block (Ph4P)2[FeIII(1-CH3im)(CN)5]·4.5H2O (1) has been synthesized. The crystal structures and magnetic properties of complexes 1 and 2 have been investigated in detail.

•Four new cyanide-bridged Cr(III)–Ni(II) complexes have been synthesized.•Four complexes have similar sandwich-like trinuclear structures.•All four complexes display overall ferromagnetic coupling.•The larger the Ni–NC bond angle, the stronger the Ni⋯Cr magnetic interaction.Four cyanide-bridged trinuclear CrIII−NiII−CrIII complexes [Ni(cyclam)][Cr(bpb)(CN)2]2·2H2O (1) (cyclam = 1,4,8,11-tetraazacyclotetradecane, bpb2– = 1,2-bis(pyridine-2-carboxamido)-benzenate), [Ni(cyclam)][Cr(bpClb)(CN)2]2·4H2O (2) (bpClb2– = 1,2-bis(pyridine-2-carboxamido)-4-chloro-benzenate), [Ni(cyclam)][Cr(bpmb)(CN)2]2·4H2O (3) (bpmb2– = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate) and [Ni(cyclam)][Cr(bpdmb)(CN)2]2 (4) (bpdmb2– = 1,2-bis(pyridine-2-carboxamido)-4,5-dimethyl-benzenate) have been synthesized by the reaction of [Ni(cyclam)](ClO4)2 with a series of dicyanidechromate(III) building blocks. Single crystal X-ray diffraction analyses show that the four complexes have similar trinuclear structures with CrIII–CN–NiII–NC–CrIII linkages. Magnetic investigations indicate the ferromagnetic coupling between Cr(III) and Ni(II) centers through the cyanide bridge, with JCrNi = 4.64(3) cm−1 for 1, 4.33(4) cm−1 for 2, 3.57(3) cm−1 for 3 and 5.3(1) cm−1 for 4. The study on magneto-structural correlation for cyanide-bridged CrIII−NiII systems reveals that the cyanide-bridging bond angle is related to the strength of magnetic exchange coupling: the larger the Ni–NC bond angle, the stronger the Ni⋯Cr magnetic interaction.Graphical abstractFour new cyanide-bridged sandwich-like trinuclear CrIII−NiII−CrIII complexes were synthesized based on a series of dicyanidechromate(III) building blocks. Magnetic investigations on the four complexes indicate the existence of ferromagnetic coupling between Cr(III) and Ni(II) centers. The study on magneto-structural correlation reveals that the larger the Ni–NC bond angle, the stronger the Ni⋯Cr magnetic interaction.

Two dinuclear cobalt(II) complexes [Co2(TPEA)2(DHBQ)](ClO4)2 (TPEA = tris(1-pyrazolylethyl)amine, DHBQ2− = deprotonated 2,5-dihydroxy-1,4-benzoquinone) (1) and [Co2(TPEA)2(DHBQ)](PF6)2 (2) with the bridged ligand DHBQ2− are synthesized which crystal structures are determined. The complexes are in the monoclinic P21/n for 1 and P21/c for 2 space group and the central Co(II) ions display distorted octahedral geometry by coordinating with the four N atoms of TPEA and the two O atoms of DHBQ in the cis positions. Complexes show a weak antiferromagnetic coupling within the Co(II) dimer with J = −1.28 cm−1, g = 2.44 for 1 and J = −1.81 cm−1, g = 2.44 for 2.

Thiazoles including five 2-arylbenzothiazoles and two 2-arylnaphthothiazoles were synthesized using a simple synthetic strategy in this work. 2-Arylbenzothiazoles and 2-arylnaphthothiazoles can be prepared by the reaction of methylaromatics with aniline or naphthylamine in the presence of elemental sulfur, respectively. All the seven thiazoles were characterized by the melting point measurement, FTIR, 1H NMR, 13C NMR and GC–MS analysis.

A new cyanide-bridged FeIIIMnIII binuclear complex {[Fe(bpy)(CN)4][Mn(TPP)(CH3OH)]}·CH3OH (1) [bpy = 2,2′-bipyridine, TPP = tetraphenylporphyrin] and an ion-pair compound {[Fe(bpy)(CN)4][Mn(TNPP)(CH3OH)2]}·2CH3CN (2) [TNPP = tetra(p-nitrophenyl)porphyrin] have been synthesized based on two manganese(III)-porphyrin precursors [Mn(L)(H2O)2]ClO4 (L = TPP and TNPP) and one cyanide-containing building block K[Fe(bpy)(CN)4]. The crystal structures of the two complexes have been determined by X-ray single crystal diffraction. Magnetic study reveals that complex 1 exhibits weak antiferromagnetic coupling between low-spin Fe(III) and high-spin Mn(III) through the cyanide bridge.A new cyanide-bridged heterobimetallic binuclear FeIIIMnIII porphyrin complex {[Fe(bpy)(CN)4][Mn(TPP)(CH3OH)]}·CH3OH (1) and an ion-pair compound {[Fe(bpy)(CN)4][Mn(TNPP)(CH3OH)2]}·2CH3CN (2) have been synthesized. The crystal structures and magnetic properties of the two complexes have been investigated in detail.Highlights► Two new FeIII–MnIII complexes containing porphyrin ligands have been synthesized. ► Complex 1 is a binuclear complex and complex 2 is an ion-pair compound. ► The magnetic properties of the two complexes have been investigated in detail.

Three cyanide-bridged FeIII–MnII binuclear complexes [Mn(phen)2Cl][Fe(bpmb)(CN)2]·H2O (1), [Mn(phen)2Cl][Fe(bpdmb)(CN)2]·H2O (2) and [Mn(phen)2Cl][Fe(bpClb)(CN)2]·3H2O·EtOH (3) [phen = 1,10-phenanthroline, bpmb2− = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate, bpdmb2− = 1,2-bis(pyridine-2-carboxamido)-4,5-dimethyl-benzenate, bpClb2− = 1,2-bis(pyridine-2-carboxamido)-4-chloro-benzenate)] have been synthesized by the reaction of Mn(phen)2Cl2 with K[Fe(L)(CN)2]. The syntheses, crystal structures and magnetic properties of the complexes have been investigated. Single-crystal X-ray diffraction analysis reveals that all three complexes are binuclear complexes and contain FeIII–C≡N–MnII linkages. Magnetic investigations indicate antiferromagnetic coupling between low-spin Fe(III) and high-spin Mn(II) centers through cyanide bridging, with JMnFe = −1.39(5) cm−1 for 1, JMnFe = −3.33(2) cm−1 for 2 and JMnFe = −1.96(5) cm−1 for 3. The magneto-structural relationships for cyanide-bridged FeIII–MnII systems are discussed based on binuclear FeIII–MnII and trinuclear FeIII–MnII–FeIII magnetic models.

A one-dimensional (1D) copper(II) complex [Cu3(μ1,1-N3)6(dmp)2]n (1) has been synthesized and structurally characterized. The molecular structure of 1 is constructed by trimeric [Cu3(μ1,1-N3)6(dmp)2] units formed through two double symmetric (basal-to-basal) end-on (EO) azide bridges and the trimeric units are connected further by double asymmetric (basal-to-apical) EO azide bridges, giving 1D chain-like structure. The chains of 1 are linked together by N–H⋯Nazide hydrogen bonds and very weak Cu⋯Nazide coordination interactions from μ-1,1,3,3-N3 fashion to form two-dimensional (2D) supramolecular architecture. The magnetic structure can be considered as uniform 1D chain formed by linear trimeric CuII–CuII–CuII units and the dominating magnetic coupling occurs within the trimeric Cu3II unit. The magnetic study shows that the compound exhibits ferromagnetic interactions with Jt = + 8.36(2) cm−1 and Jc = + 0.35(4) cm−1 for intratrimeric and intertrimeric Cu3II unit based on 1D magnetic model, respectively.Highlight► A new copper(II) complex [Cu3(μ1,1-N3)6(dmp)2]n (1) has been synthesized and characterized. ► The molecular structure of 1 is 1D chain bridged by different double end-on azide bridges. ► The magnetic study shows that the compound exhibits overall ferromagnetic interactions. ► The magnetic susceptibilities of 1 have been fitted based on two magnetic models.

Three dicyanide-containing building blocks and one manganese(III) compound based on bicompartimental Schiff base ligand have been employed to assemble cyanide-bridged heterometallic complexes, resulting in three cyanide-bridged MIII–MnIII (M = Fe, Cr, Co) complexes: K{{[Mn(L)(CH3OH)][Fe(bpb)]}2}ClO4·H2O (1), K{{[Mn(L)(CH3OH)][Cr(bpb)]}2}ClO4·CH3OH (2) and K{{[Mn(L)(CH3OH)][Co(bpb)]}2}ClO4·H2O (3) (bpb2− = 1,2-bis(pyridine-2-carboxamido)benzenate, L = N,N-ethylene-bis(3-methoxysalicylideneiminate). Single X-ray diffraction analysis shows their very similar pentanuclear structures consisting of two same units {[Mn(L)(CH3OH)][Fe(bpb)]} linked by K+ complexed to eight phenolic oxygen atoms. The coordination geometry for both of the M(III) and Mn(III) ion in all the complexes is a slightly distorted octahedron. Investigation over magnetic properties of complexes 1 and 2 reveals the antiferromagnetic magnetic coupling between the neighboring Fe(Cr)(III) and Mn(III) ions through the bridging cyanide group. A best-fit to the magnetic susceptibilities of these two complexes leads to the magnetic coupling constants J = −1.65(2) (1) and −0.99(1) cm−1 (2), respectively.Graphical abstractThree dicyanide-containing building blocks and one manganese(III) compound based on bicompartimental Schiff base ligand have been employed to assemble cyanide-bridged heterometallic complexes, resulting in three pentanuclear cyanide-bridged MIII–MnIII (M = Fe, Cr, Co) complexes. Investigation over magnetic properties of complexes 1 and 2 reveals the antiferromagnetic magnetic coupling between the neighboring Fe(Cr)(III) and Mn(III) ions through the bridging cyanide group.Highlights► Three pentanuclear cyanide-bridged heterometallic complexes are reported. ► Single X-ray structure analysis of the three complexes are carried out. ► Magnetic properties of the complexes are investigated.

Four pyridinecarboxamide iron dicyanide building blocks and one Mn(III) compound have been employed to assemble cyanide-bridged heterometallic complexes, resulting in a series of trinuclear cyanide-bridged FeIII–MnII complexes: {[Mn(DMF)2 (MeOH)2][Fe(bpb)(CN)2]2}·2DMF (1), {[Mn(MeOH)4][Fe(bpmb)(CN)2]2}·2MeOH·2H2O (2), {[Mn(MeOH)4][Fe(bpdmb)(CN)2]2}·2MeOH·2H2O (3) and {[Mn(MeOH)4][Fe(bpClb)(CN)2]2}·4MeOH (4) (bpb2− = 1,2-bis(pyridine-2-carboxamido)benzenate, bpmb2− = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate, bpdmb2− = 1,2-bis(pyridine-2-carboxamido)-4,5-dimethyl-benzenate, bpClb2− = 1,2-bis(pyridine-2-carboxamido)-4-chloro-benzenate). Single-crystal X-ray diffraction analysis shows their similar sandwich-like structures, in which the two cyanide-containing building blocks act as monodentate ligands through one of their two cyanide groups to coordinate the Mn(II) center. Investigation of the magnetic properties of these complexes reveals antiferromagnetic coupling between the neighboring Fe(III) and Mn(II) centers through the bridging cyanide group. A best fit to the magnetic susceptibilities of complexes 1 and 3 gave the magnetic coupling constants J = −1.59(2) and −1.32(4) cm−1, respectively.