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The design and preparation of chiral metal-organic frameworks (CMOFs) from achiral ligands are a big challenge. Using 3-nitro-4-(pyridin-4-yl)benzoic acid (HL) as a new linker, a total of eight chiral lanthanide-organic frameworks (LOFs), namely poly[diaquatris[μ2-3-nitro-4-(pyridin-4-yl)benzoato-κ2 O:O′]-lanthanide(III)], l- and d-[Ln(C12H7N2O4)3(H2O)2]n [(1), Ln = Eu; (2), Ln = Gd; (3), Ln = Dy, (4), Ln = Tb], were hydrothermally synthesized without chiral reagents and determined by X-ray crystallography. Crystal structure analyses show that l-(1)-(4) crystallize in the hexagonal P65 space group and are isomorphous and isostructural, while the enantiomers d-(1)-(4) crystallize in the hexagonal P61 space group. All LnIII ions are octacoordinated by six carboxyl O atoms of six 3-nitro-4-(pyridin-4-yl)benzoate ligands and two water molecules in a dodecahedral geometry. A one-dimensional neutral helical [Ln2(CO2)3]n chain is observed in (1)-(4) as a chiral origin. These helical chains are further interconnected via directional hydrogen-bonding interactions between pyridyl groups and water molecules to construct a three-dimensional (3D) homochiral network with hex topology. The present CMOF structure is the first chiral 3D hydrogen-bonded hex-net and shows good water stability. Solid-state circular dichroism (CD) signals revealed that (1)-(4) crystallized through spontaneous resolution. Furthermore, (1) and (4) display a strong red and green photoluminescence at room temperature, respectively, but their intensities reduce to almost half at 200 °C. Notably, upon excitation under visible light (463 nm), a circularly polarized luminescence (CPL) of (1) in the solid state is observed for the first time, with a glum value of 2.61 κ 10×-2. [ABSTRACT FROM AUTHOR]

One novel cyanide-bridged mixed-valence {FeIII 2 (μ -CN) 4 FeII 2 } square cluster exhibits thermally-induced, reversible, complete spin transition behaviour at two out of four metal centers. • One novel cyano-bridged mixed-valence bimetallic {FeIII 2 (μ -CN) 4 FeII 2 } cluster has been prepared. • The square cluster exhibits thermally-induced, reversible, complete spin transition behavior. One novel cyano-bridged mixed-valence bimetallic {FeIII 2 (μ -CN) 4 FeII 2 } cluster, {[(Tp)FeIII(CN) 3 ] 2 [FeII(Py 2 N 2)] 2 }·(PF 6) 2 (1), has been synthesized (Tp = hydrotris(pyrazolyl)borate, Py 2 N 2 = N,N'-bis(2-pyridylmethyl)-N,N'-bis(4-benzyl)-1,2-ethanediamine). The molecular structure has been determined by single-crystal X-ray diffraction. Compound 1 exhibit temperature driven Fe(II) spin crossover behaviour (SCO) associated with the high-spin (HS) ↔ low-spin (LS) transition with the transition temperature of 130 K at two out of four metal centers. The evolution of HS and LS Fe(II) ions with temperature was followed by FT-IR, X-ray crystallography, the variable temperature magnetic susceptibility. [ABSTRACT FROM AUTHOR]