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A versatile microporous metal-organic framework (MOF), {[Cu(TIA)]·1.5CH3OH}n (Cu-1), was successfully obtained via the solvothermal reaction of cuprous(II) salt with the bifunctional ligand 3-(1H-1,2,4-triazol-1-yl)isophthalic acid. Single-crystal X-ray diffraction studies indicate that Cu-1 contains an apo three-dimensional skeleton and two types of one-dimensional channels. The framework of Cu-1 has excellent acid-alkali resistance and thermal stability, which is stable in a pH = 2-13 aqueous solution and an 260 °C air environment. In addition, the microporous copper MOF shows very high uptakes of CO2 (180 cm3·g-1) and C2H2 (113 cm3·g-1) at 273 K and displays excellent adsorption selectivity for small molecular gases. The ideal adsorbed solution theory selectivity values for C2H2/C2H4, CO2/CH4, and CO2/N2 are 2, 9, and 22 at 298 K, respectively. At the same time, breakthrough experiments for CO2/CH4, CO2/N2, and C2H2/C2H4 were further conducted to verify the efficient separation performances.

Photodegradation of organic dyes over coordination polymer (CP) photocatalysts has become one of the effective strategies for the prevention and control of water pollution, in which the energy band...

Two new complexes, Ln(hfac)3(NITPhOA)2 (Ln = Tb(1), Dy(2); NITPhOA = 2-(4′-amyloxyphenyl)−4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide; hfac = hexafluoroacetylacetonate) have been synthesized and characterized. Single crystal X-ray diffraction analysis reveals that both complexes show mononuclear tri-spin structures. The central Ln(III) ion is eight-coordinated by three hfac anions and two NITPhOA molecules, in which the NITPhOA radical acts as monodentate ligand through the NO groups, and the Ln(III) center exhibits a dodecahedron environment. It's interesting that the mononuclear units form a pseudo-one-dimensional chain structure through intermolecular non-covalent N–O⋯O–N contacts of nitroxide groups for 1. Alternating current (ac) magnetic susceptibilities show a frequency-dependent characteristic for both 1 and 2, typical of slow relaxation of magnetization. It's the first time for a lanthanide–radical complex to form a pseudo one-dimensional structure through non-covalent O⋯O contacts.

Three new lanthanide complexes based on a nitronyl nitroxide radical [Ln(hfac)3(NIT3Ph3Py)]2 (Ln = Dy(1), Tb(2), Gd(3); hfac = hexafluoroacetylacetonate, NIT3Ph3Py = 2-(3′-(3″-pyridyl)-phenyl)-4,4,5,5- tetramethylimidazoline-1-oxyl-3-oxide) have been successfully synthesized, characterized structurally and magnetically. Single crystal X-ray diffraction analysis reveals that complexes 1–3 are isomorphous in which NIT3Ph3Py acts as a bridging ligand linking two Ln(III) ions through the nitrogen atom of pyridine ring and the oxygen atom of N O group to form a four-spin system. The magnetic studies reveal that the ferromagnetic interactions between the Ln(III) ions and nitronyl nitroxide radicals in the complexes. Moreover, alternating current (ac) magnetic susceptibilities show that Dy(III) complex exhibits frequency-dependent signals at low temperature.

Multinuclear hetero-tri-spin complexes based on a methyl-pyrazole nitronyl nitroxide radical, namely, [Ln2Cu3(hfac)12(4-NIT-MePyz)4] (Ln = Gd(1), Tb(2), Dy(3); hfac = hexafluoroacetylacetone; 4-NIT-MePyz = 2-{4-(1-methyl)-pyrazolyl}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) have been successfully obtained through a one-pot reaction of the radical ligand (4-NIT-MePyz) with Cu(hfac)2 and Ln(hfac)3. These 2p–3d–4f complexes exhibit five-nuclear structures with the sequence [Cu–Rad–Ln–Rad–Cu–Rad–Ln–Rad–Cu], in which each 4-NIT-MePyz radical acting as a bidentate bridging ligand is coordinated to one Ln(hfac)3 unit through one oxygen atom of the NO groups and to one Cu(hfac)2 unit with one nitrogen atom from the pyrazole ring. For complex 1, based on the spin Hamiltonian calculations and MAGPACK program, it is concluded that there exist ferromagnetic couplings between GdIII and NIT radicals, as well as between CuII and free radicals with J1 = 6.8(1) and J3 = 1.3(2) cm−1, respectively, and antiferromagnetic interactions between radical and radical with J2 = −2.8(5) cm−1. Complex 2 shows frequency-dependent out-of-phase signals under a zero or 2000 Oe dc field indicating single-molecule magnetic behavior.

The combination of LnIII ions (GdIII, TbIII or DyIII) and a pyrazole nitronyl nitroxide radical results in three isomorphous complexes, namely, [Ln(hfac)3(NIT-Pyz)]2 (Ln = Gd(1), Tb(2), Dy(3); hfac = hexafluoroacetylacetone; NIT-Pyz = 2-{3-pyrazolyl}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide). Single crystal X-ray diffraction studies revealed that all of them are composed of two crystallographically independent mononuclear systems, in which the central LnIII ions are coordinated by three hfac and one bidentate chelating NIT-Pyz radical. The central LnIII ions are all in square antiprism geometry (D4d) polyhedron configurations. Based on the spin Hamiltonian calculations, there exist antiferromagnetic couplings in the GdIII-NIT radical system in complex 1. Complexes 2 and 3 show frequency-dependent out-of-phase signals in a zero field indicating single-molecule magnetic behavior. Moreover, Tb's complex (2) shows a single thermal relaxation process with an energy barrier of 26 K. For Dy's complex (3), the Orbach and Raman processes both contribute to the magnetic relaxation behaviors.

A dynamic microporous magnet shows reversible temperature-tuned single-crystal-to-single-crystal transformations by stepwise losing of coordinated and lattice water molecules, exhibiting an unusually observed room-temperature hysteresis loop, variable magnetic ordering temperatures and high adsorption selectivity for CO2 over N2.

Prussian Blue Analogues Mn3[Fe(CN)6]2·12H2O porous nanoparticles have been achieved by coprecipitation method and using polyvinyl pyrrolidone (PVP) as a protective matrix. The obtained nanoparticles were characterized by X-ray diffraction (XRD), infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TG), scanning electron microscopy (SEM), and high resolution transmission electron microscopy (HRTEM). The X-ray diffraction measurement results show that all the obtained nanoparticles are face centered cubic structure. The infrared spectroscopy (IR) and X-ray photoelectron spectroscopy (XPS) measurement results indicate that Mn3[Fe(CN)6]2·12H2O nanoparticles are mixed-valence, and the ratios of MnIIFeIII to MnIIIFeII in obtained nanoparticles are different in water and water-methanol mixed solvent. The magnetic studies of nanocubes (about 480 nm, coming from water synthesis) and nanospheres (about 200 nm, from co-solvent synthesis) materials show that both samples have spin-glass behavior, but magnetic property measurement results indicated Tc, Tb and Tg temperatures of Mn3[Fe(CN)6]2·12H2O decreases as the size of nanoparticle reduces.

Four unique infinite 2D Mn(II) aggregates, [Mn 3 ( μ 3 -ade) 2 (OAc) 4 X] n (X = DMF for 1 , DMA for 2 and C 2 H 5 O − for 3 ), [Mn 3 ( μ 3 -ade) 2 (ap) 2 DMF] n ( 4 ) (Hade = adenine; DMF = N , N- dimethylformamide; DMA = N , N- dimethylacetamide, OAc − = acetate ion, H 2 ap = adipic acid) with trinuclear Mn(II) as secondary building units (SBUs), have been successfully synthesized by the assembly of Hade nucleobase and manganese acetate under solvothermal conditions. The resultant complexes can be applied to explore the influence of solvent or co-ligands on the self-assembly and properties of metal complexes based on adenine. The Hade represent tridentate μ 3 -N3, N7, N9 bridging coordination modes. The acetate anions exhibit μ 2 - η 1 :η 1 bidentate, μ 2 - η 1 :η 2 tridentate mode, and μ 2 - η 0 :η 2 bidentate mode. The adipate anions in complex 4 adopt two coordination modes: one is μ 4 - η 2 :η 1 :η 1 :η 1 pentadentate mode, the other one is μ 3 - η 1 :η 2 :η 2 :η 1 hexadentate mode. Their magnetic behaviors exhibit interesting variations, in which the local net magnetization at low temperature increases from 1 to 3 . The Mn II 3 SBUs in 1 – 3 are symmetric with an inversion center, whereas that in 4 has three crystallographically independent Mn II atoms. Thus, the magnetic behaviors of 4 are different from complex 1 – 3 .

Two water-stable silver(I) cation metal organic frameworks (MOFs), namely 2D MOF {[Ag(L)2]BF4}n (1) and 3D MOF {[Ag3(L)3]·(H2O)·(CF3SO3)3}n (2) (L = 1-(4-aminobenzyl)-1,2,4-triazole), have been prepared. 1 is the first example of a 2D MOF-based sensor for real-time discrimination of L- and D-cysteine from other amino acids through the quenching effect. Through deliberately tuning the nanoparticles of 2 under ultrasound conditions, these nanoparticles are, for the first time, successfully applied as an excellent DNA detecting platform.

• Two novel ternary Zn II -triazole-polycarboxylate framework has been synthesized and characterized.

A novel (4, 12)-connected metal-organic framework, {(NH4)2·[Co11(μ4-OH)6(CN)6(trz)12]}n, was solvothermally constructed from unusual CoII8 cubes, octahedral CoII1 subunits, and μ3-N1,N2,N4-triazolate (trz) connectors. Strong antiferromagnetic coupling between the neighboring CoII ions results in an absence of long-range magnetic ordering, leading to a strong spin-frustration with f > 62.

A field-induced MnIII-based single-ion magnet with axially elongated Jahn–Teller distortion was well isolated in a layered complex by diamagnetic NaI ions, which exhibits an effective thermal-activated energy barrier of 12.9 cm− 1 under 2.0 kOe dc field resulting from strongly axial anisotropy of the high-spin MnIII ion.

Two 4-(1H-1,2,4-triazol-1-yl)phenol (hptrz)-based transition metal complexes with different aromatic polycarboxylic acids as co-ligands, {[Cu2(H2O)4(hptrz)2(btec)]⋅2H2O}n (1) and [Cu(hptrz)2 (H2btc)2]·H2O (2) (H4btec = benzene-1,2,4,5-tetracarboxylic acid, H3btc = benzene-1,3,5-tricarboxylic acid), have been obtained, which were structurally characterized by single-crystal X-ray diffraction, elemental analysis, FT-IR spectra, thermogravimetric curves and luminescence spectra in detail. Structural analysis reveals that 1 is a 1-D infinite chain framework extended by btec4– anions, whereas 2 is isolated centrosymmetric mononuclear entities. In contrast, the neutral hptrz is a terminal ligand to complete the metal coordination sphere and it also helps to assemble the low-dimensional coordination sphere into a high-dimensional supramolecular architecture by O–H···O hydrogen-bonding interactions. Additionally, the high stability and luminescence emission suggest that 1 and 2 are good candidates for light emission materials. The magnetic features of 1 may be due to weak antiferromagnetic coupling between CuII ions which are separated by btec4– anions.

A new nitronyl nitroxide-Tb(III) complex, [Tb(hfac)3(NIT-3-Br-4Py)2] (1) (hfac = hexafluoroacetyl -acetonate, NIT-3-Br-4Py = 2-(3′-bromo-4′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide), has been synthesized and characterized. The single-crystal X-ray diffraction analysis shows it crystallizes in monoclinic C2/c space group, and is composed of mononuclear molecules. The central Tb(III) ion is eight-coordinated by three bidentate chelating hfac anions and two monodentate NITR ligands, with a dodecahedron environment. Ac magnetic susceptibility study shows that complex 1 exhibits slow magnetic relaxation, suggesting single-molecule magnet behavior.

Two methylammonium-templated metal vanadates, namely [CH3NH3]2MV2O7 (M = Mn (1) and Cd (2)), have been solvothermally synthesized and characterized by IR, TGA, UV–Vis, single-crystal X-ray diffraction (XRD) and Powder XRD, etc. These two isostructural compounds feature an open-framework structure constructed by MO6 octahedra and V2O7 dimers. The methylammonium cations are located in the channels of the framework and act as bi-functional charge-compensating and structure-directing agents. Compound 1 exhibits an effective adsorption performance towards Eu3+ by means of ion exchange. Magnetic study reveals the antiferromagnetic exchange between Mn2+ ions in compound 1.

The combination of LnIII ion (GdIII or DyIII) with two different indazole nitronyl nitroxide radicals results in four novel 2p–4f compounds, namely, [Ln(hfac)3(5-IndazoleNIT)]2 (Ln = Gd (1), Dy (2); hfac = hexafluoroacetylacetone; 5-IndazoleNIT = 5-(1′-oxyl-3′-oxido-4′,4′,5′,5′-tetramethyl-4,5-hydro-1H-imidazol-2-yl)-1H-Indazole) and [Ln(hfac)3(6-IndazoleNIT)]2 (Ln = Gd (3), Dy (4); 6-IndazoleNIT = 6-(1′-oxyl-3′-oxido-4′,4′,5′,5′-tetramethyl-4,5-hydro-1H-imidazol-2-yl)-1H-Indazole). Single crystal X-ray diffraction studies revealed that compounds 1–2 are binuclear isostructural complexes with local D2d symmetry, in which each 5-IndazoleNIT molecule acts as a bridging ligand linking two LnIII ions through the oxygen atom of its NO group and nitrogen atom of its indazole ring to form a cyclic four-spin system. Complexes 3–4 exhibit analogous binuclear cyclic four-spin systems, where the symmetry of central LnIII ions is D4d due to the change of location of the NO group in the indazole ring. In addition, compound 2 displays no out-of-phase alternating-current (ac) signal, whereas compound 4 exhibits obvious slow relaxation of magnetization, suggesting single-molecule magnet (SMM) behavior. The different magnetic relaxation behaviour between 2 and 4 is largely dependent on the ligand field of the central dysprosium ions.

Hydrothermal reaction of zinc oxide, 1,2-benzenedicarboxylic acid (H2pa) and 1,2,4-triazole (Htrz) yielded a (3,12)-connected 2-D coordination network [Zn8(trz)4(OH)4(pa)4]n (1), in which rare tetragonal prism-like ZnII8 clusters and tridentate 1,2-benzenedicarboxylate act as 12- and 3-connected nodes, respectively. Moreover, the luminescent emission spectra and thermostability of 1 have been investigated.

Three oximato-based oligomeric metal complexes, {[Cu3(H2O)(µ3-OH)(mpko)3(NO3)]·3H2O·NO3} (1), {[Cu6(μ3-OH)2(mpko)6(Br)4]·8H2O} (2), and {[Fe3(mpko)6]·ClO4·2.5CH3CN} (3) (mpkoH = 1-(pyrazin-2-yl)ethanone oxime), were synthesized by varying different spin carriers, and structurally and magnetically characterized. Structural determinations reveal that 1 is a discrete triangular {Cu3(μ3-OH)}5+ molecule with two adjacent metal ions further bridged by chelating-bridging mpko− ligands. Complex 2 features a centrosymmetric hexanuclear entity with two triangular {Cu3(μ3-OH)}5+ subunits extended by a pair of bridging μ-Br− anions. By contrast, 3 exhibits an approximately linear trinuclear entity with central FeIII ion connected with two external FeII ions by six crystallographically unique mpko− ligands. Strong antiferromagnetic interactions with the coupling constant up to 223(1) cm−1 are observed in the triangular subunits of 1 and 2. In 3, the central FeIII ion with S = 5/2 is almost magnetically isolate...

Five new nitronyl-nitroxide radical-Ln(III) complexes, [Ln(hfac)3(NITPh-2-OCH2Ph)(IMHPh-2–OCH2Ph)] (Ln = Tb(1), Dy(2)) and [Ln(hfac)3(NITPh-2-OCH2Ph)2] (Ln = Ho(3), Er(4), Yb(5)) (hfac = hexafluoroacetylacetonate, NITPh-2-OCH2Ph = 2-(2-benzyloxyphenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, IMHPh-2-O-CH2Ph = the reduced derivative of NITPh-2-OCH2Ph), have been synthesized and characterized. The single-crystal X-ray diffraction analysis shows that all these complexes crystallize in triclinic P 1 − space group, and are composed of mononuclear molecules. The central Ln(III) ion is eight-coordinated by three bidentate chelating hfac anions and two monodentate NITR (or IMHR) molecules, with a dodecahedron environment. There arise a common interesting structural feature for these complexes that the mononuclear molecules form pseudo-binuclear structures through intermolecular non-covalent N–O⋯O–N contacts of nitroxide groups. All of them show intramolecular weak antiferromagnetic interactions between Ln(III) ion and radicals. Alternating current (ac) magnetic susceptibilities display a frequency-dependent characteristic for both Tb(1) and Dy(2), typical of magnetic slow relaxation of single-molecule magnet (SMM) behavior.

The first tetranuclear metallacage and mononuclear cocrystalline DyIII-radical complex was synthesized and characterized. The metallacage in [Dy4(hfac)8(IMPhThio)2(OH)4][Dy(hfac)3(NITPhThio)2] consists of Dy(hfac)2+ groups bridged by OH– and the IMPhThio radical. Field-induced single-molecule-magnet behavior was observed in the nitronyl nitroxide radical-bridged polynuclear complex.

Disc-like CoII7 core-derived (4,4)- and (3,6)-connected layers, {[Co7(C2H5OH)1.5(H2O)0.5(Hdatrz)2(μ3-OH)4(ip)5]·2.5H2O·C2H5OH}n (1) and [Co7(H2O)4(ade)2(μ3-OH)6(sip)2]n (2) (Hdatrz = 3,5-diamino-1,2,4-triazole, ade− = adeninate, ip2− = isophthalate and sip3− = 5-sulfoisophthalate) were solvothermally generated and structurally and magnetically characterized. The effect of magnetic anisotropy and exchange coupling from the local CoII7 cores on the resulting magnetism properties are discussed. A crystallographically asymmetric CoII7 core in 1 exhibited an unusual single-molecule magnet (SMM)-like response under zero dc field resulting from strong anisotropy generated by two different types of CoII polyhedra and highly anisotropic exchange interactions. By contrast, a highly symmetric CoII7 disc in 2 belonging to the C2h point group showed only strong ferromagnetic exchange, to lead to an overall ST = 7/2 spin ground-state at low temperature. Thus, the interplay of magnetic anisotropy and exchange coupling has a great and complicated influence on the overall magnetic phenomena, which should be fully considered for the design and preparation of new CoII-SMMs.

Four magnetic MOFs with anisotropic CoII ions, {[Co5(H2O)2(μ3-OH)2(atz)2(stp)2]·1.5H2O}n (1), {[Co5(H2O)2(μ3-OH)2(trz)2(stp)2]·1.3H2O}n (2), {[Co5(H2O)6(μ3-OH)2(trz)2(stp)2]·2.5CH3OH}n (3) and {[Co3(H2O)4(Hdatrz)2(stp)2]·3H2O}n (4) (stp3− = 2-sulfoterephthalate, trz− = 1,2,4-triazolate, atz− = 3-amino-1,2,4-triazolate and Hdatrz = 3,5-diamino-1,2,4-triazole) were solvothermally isolated by varying the substituent groups appended on the N-heterocyclic triazole and structurally and magnetically characterized. Structural analyses indicate that the former two complexes are crystallographically isostructural, exhibiting pillared-layer frameworks with mixed triazolyl and carboxylate extended CoII4 + CoII1 layers supported by rigid stp3− connectors. Complex 3 is built from butterfly-shaped CoII4 cluster-based layers, which are interconnected with single cobalt(II) octahedra by ditopic stp3− bridges. By contrast, complex 4 consists of linear {Co3(μ-N1,N4-Hdatrz)2} subunits, which are extended by 3-connected stp3− linkers into a stable 3D framework. Magnetically, 1 exhibits ferromagnetic ordering below 2.7 K due to the well-organized alignment of the non-compensated resultant moment from octahedra and tetrahedral cobalt(II) carriers, while 3 is in a non-zero paramagnetic state above 2.0 K resulting from the coexistence of intermetallic ferromagnetic and antiferromagnetic interactions. The magnetic competition between weak inter-subunit antiferromagnetic interactions and the external magnetic field makes 4 behave as a field-induced metamagnet with a critical field of 27.5 kOe. These interesting magnetostructural results suggest that the anisotropy of the moment carrier and the interlayer/intersubunit separations significantly dominate the magnetic responses in extended MOFs, providing an informative platform for the further development of interesting magnetic materials, both of academic and industrial interest.

A new oxime-derived {DyIII4NiII6} cluster with a paramagnetic butterfly-shaped DyIII4 core and peripheral diamagnetic planar-square NiII ions was solvothermally synthesized. The weak ferromagnetically coupled cluster exhibits field-induced single-molecule magnetic behavior with two thermally activated single-ion relaxations.

The combination of LnIII ions (GdIII, TbIII or DyIII) with a triazole nitronyl nitroxide radical results in six novel 2p–4f compounds, namely, [Ln2(hfac)6(MeTrzNIT)(H2O)2]·1/2CH2Cl2 (Ln = Gd(1), Tb(2), Dy(3); hfac = hexafluoroacetylacetone; MeTrzNIT = 2-[3-(5-methyl-l,2,4-triazolyl)]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide and [Ln(Phtfac)3(MeTrzNIT)]2·C7H14·3H2O (Ln = Gd(4), Tb(5), Dy(6); Phtfac = 4,4,4-trifluoro-1-phenylbutane-1,3-dione). Single crystal X-ray diffraction studies revealed that compounds 1–3 are binuclear isostructural complexes, in which one MeTrzNIT molecule acts as a double-bridging ligand coordinated to two LnIII ions through its two NO groups and two nitrogen atoms of the triazole ring. In 1–3, the coordination number around the lanthanide ion is nine, and the polyhedron is a 4,4,4-tricapped trigonal prism (D3h). While the larger steric hindrance of the Ph- group than CF3- in the Phtfac ligand induces complexes 4–6 to be mononuclear bi-spin compounds, in which central LnIII ions are coordinated by three Phtfac and one bidentate MeTrzNIT radical. The coordination number around the lanthanide ion in 4–6 is eight, and the polyhedron is in a square antiprism geometry (D4d). Compounds 3 and 5 were found to exhibit slow relaxation of the magnetization, suggesting single-molecule magnet (SMM) behavior, while no ac signal is noticed for compounds 2 and 6. The different magnetic relaxation behaviours between 2 and 5, or between 3 and 6, are due to the different crystal structures around the LnIII ions and the magnetic interaction. It is demonstrated that the β-diketonate coligand may play an important role in determining the spin dynamics for the lanthanide-radical system.

Three series of six pyrazine-2-amidoxime (H2pzaox)-based 3d–4f clusters, {Ln8Ni6}, {Ln5Ni10} and {Ln5Ni8} (Ln = Dy and Gd), were solvothermally synthesized in the absence or presence of different coligands, and were structurally and magnetically characterized. The unusual ring-shaped {Ln8(μ3-OH)4} core in the two {Ln8Ni6} complexes is generated by four corner-sharing triangle {Ln3(μ3-OH)} units, which are further connected to six outer NiII ions by twelve deprotonated H2pzaox ligands in three common binding modes. By contrast, the remaining four clusters contain only two corner-sharing {Ln3(μ3-OH)} triangles, which interact with peripheral NiII ions through fourteen H2pzaox ligands in five (for {Ln5Ni10}) and four (for {Ln5Ni8}) different bridging ways. Thus, the interesting core motifs observed in these clusters depend significantly on the number of the triangular {Ln3(μ3-OH)} subunits and their connectivity manner with the singly and doubly deprotonated pyrazine-2-amidoxime ligand. Additionally, weak ferromagnetic superexchange in the {Dy5Ni10} and {Ln5Ni8} clusters and antiferromagnetic coupling in {Ln8Ni6} and {Gd5Ni10} clusters was respectively mediated by versatile oximate bridges between the intramolecular LnIII and NiII ions. Furthermore, the three DyIII-derived aggregates exhibit slightly temperature-dependent magnetic relaxations under a zero dc field, and the three GdIII-based clusters display large magnetic entropy changes of 23.5 J kg−1 K−1 for {Gd8Ni6}, 19.4 J kg−1 K−1 for {Gd5Ni10}, and 22.4 J kg−1 K−1 for {Ln5Ni8} at 4.0 K and 70 kOe. These interesting results are helpful for the understanding of oximate-based 3d–4f coordination chemistry and their structure–function relationships.

A self-catenated Zn(II)-organic framework formulated as [Zn2(3,3′-bpeab)(oba)2]·DMF (1) exhibiting a six-connected 44·610·8 topology has been successfully synthesized through the mixed-ligand of kinked 3,3′-bis[2-(4-pyridyl)ethenyl]azobenzene (3,3′-bpeab) and 4,4′-oxybis-benzoic acid (H2oba) under solvothermal condition. UV light triggers isomerization of complex 1 in a single-crystal-to-single-crystal (SCSC) manner, giving rise to a conformational supramolecular isomer 1_UV through the pedal motion of photoresponsive double bonds. Dynamic photo-switching in the obtained light-responsive supramolecular isomers leads to instantly reversible CO2 uptake. Furthermore, the ligand originated fluorescence emission of water-resistant complex 1 is selectively sensitive to 4-nitrotoluene (4-NT) owing to a higher quenching efficiency of the perilous explosive over other structurally similar nitroaromatics, prefiguring the potentials of 1 as a fluorescence sensor towards 4-NT in aquatic media.

Two 3-amino-1,2,4-triazole (Hatz)-based magnetic complexes, {[Mn3(H2O)2(Hatz)2(sip)2]·2H2O}n (1) and {[Mn(H2O)3(Hatz)(bda)]·H2O}n (2) (sip3− = 5-sulfoisophthalate and bda2− = trans-butenedioate), were respectively prepared by varying dicarboxylate-containing coligands, and were structurally and magnetically characterized. Structural determinations reveal that 1 exhibits a two-dimensional layered structure with linear {Mn3(μ-N1,N2-Hatz)2}6+ subunits extended by tritopic sip3− connectors. By contrast, 2 is an infinite zigzag chain constructed from octahedral Mn(II) ions and μ-N1,N4-Hatz linkers. Magnetically, typically antiferromagnetic interaction observed in the local MnII3 subunit of 1 mediated by mixed μ-syn, syn-COO− and μ-N1,N2-Hatz heterobridges is slightly stronger than that of 2 transmitted by single μ-N1,N4-Hatz mediator.