•Complex 1 possessed a threefold interpenetrated 3D 6-connected pcu net based on dimeric [Co2(COO)2]2– unit.•Complex 2 displayed a 3D 8-connected framework with 416.611.8 topology based on trinuclear [Mn3(COO)6] subunits.•The factors regulating the structures of the complexes were discussed.•Magnetic analyses show that weak antiferromagnetic interactions exist within the binuclear Co(II) and trinuclear Mn(II) units.Two mixed-ligand coordination polymers, namely, {[Co(oba)(4-bpdb)]·CH3OH}n (1), and {[Mn3(oba)3(4-bpdb)(DMF)2]·4H2O}n (2) (H2oba = 4,4′-oxybis-benzoate, 4-bpdb = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene), were synthesized under solvothermal conditions. The structure of 1 possessed a three-fold interpenetrated 3D 6-connected pcu topology based on dimeric [Co2(COO)2]2 − units. While 2 displayed a uninodal 3D 8-connected net with 416.611.8 topology based on trinuclear [Mn3(COO)6] subunits. Magnetic analyses indicate that both two compounds show weak antiferromagnetic interactions within binuclear Co(II) and trinuclear Mn(II) units.Two coordination polymers are reported: complex 1 possessed a threefold interpenetrated 3D 6-connected pcu topology based on dimeric [Co2(COO)2]2 − units, while 2 displayed a uninodal 3D 8-connected net with a 416.611.8 topology based on trinuclear [Mn3(COO)6] subunits. The magnetic properties of the compounds were explored.Download high-res image (251KB)Download full-size image

Three isomorphous metal–organic complexes with 1H-tetrazolyl-acetic acid (TAA), namely [M(TAA)2]n (M = MnII, 1, CoII, 2 and NiII, 3), have been synthesized under hydrothermal conditions. All the compounds were fully characterized by X-ray crystallography, elemental analysis, IR spectroscopy, thermal analysis and magnetic studies. The single crystal X-ray analyses show that the 1D chains of [M(COO−)2]n (M = MnII, 1, CoII, 2 and NiII, 3) are further joined by tetrazolyl spacers to form a 3D network. Based on the topological perspective, the complexes can be simplified into a (3,6)-connected 2-nodal net with (42.6)2(44.62.88.10) “ant” topology. The magnetic measurements reveal different magnetic exchange-coupling interactions: antiferromagnetic for 1 and ferromagnetic for 2 and 3. Furthermore, the magnetic measurements confirm that spin glass behaviour occurs in 3 but not in 2.

Six new highly symmetrical and isostructural 3D lanthanide metal–organic frameworks (Ln-MOFs) {[Ln2(Ccbp)3·6H2O]·3Cl−·4H2O} Ln = Tb (1), Eu (2), Gd (3), Sm (4), Er (5) and Yb (6), Ccbp− = 4-carboxy-1-(4-carboxybenzyl)pyridinium, and the mixed Ln-MOF {[Tb1.828Eu0.172(Ccbp)3·6H2O]·3Cl−·4H2O} (7) have been successfully synthesized and fully characterized. The complex 1 was utilized as a representative chemosensor to detect small molecules, cations and anions, respectively. Interestingly, 1 exhibited dual-functional detection of Pb2+ and Fe3+ ions in ethanol with excellent linear variation to quantify the corresponding concentration change. In addition, the temperature-dependent luminescence properties of 1, 2 and 7 have also been investigated systematically, which demonstrated that both 1 and 7 have potential to quantitatively detect temperature as a luminescent thermometer over a wide range from 10–300 K for 1 and 10–170 K for 7. Thus, the as-obtained Ln-MOF materials have potential to serve as the first examples of a multifunctional luminescent sensor for quantitatively detecting the temperature (10–300 K) and the concentration of Pb2+ and Fe3+ ions in ethanol solution.

•Complex 1 has a unique 2D double-layered framework containing rhombic tetrameric Zn(II) of mixed Td and Oh geometries.•Complex 2 shows a 2D + 2D → 3D parallel polycatenated framework with cuboids as the fundamental building units.•Complex 3 possess an interesting 2D → 3D inclined polycatenation net based on 44-sql subunits.•The photoluminescent properties of 1 and 2, and magnetic properties of 3 were studied.Three metal–organic networks, namely, [Zn2(Hnip)(4-bpdb)(nip)2(μ3-OH)] (1), {[Zn(tbip)(4-bpdb)1.5]·CH3OH}n (2), and {[Ni(1,3-bdc)(4-bpdb)]·2H2O}n (3) (4-bpdb = 1.4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene, H2nip = 5-nitroisophthalic acid, H2tbip = 5-tert-butylisophthalic acid, and 1,3-H2bdc = 1,3-benzenedicarboxylic acid) are synthesized under hydrothermal conditions. The structure of 1 is built around uncommon rhombic {Zn4} clusters with double Td and double Oh Zn(II) geometries, which extend into a 2D network by the rigid deprotonated H2nip and 4-bpdb bridges. Meanwhile, 2 presents a novel 2D → 3D parallel polycatenated framework assembled from 2D bilayers with cuboids as the fundamental building units. Compound 3 features an interesting 2D → 3D inclined polycatenated network based on 44-sql subunits. Moreover, the thermal stabilities, photoluminescence, and magnetic properties of the compounds are also discussed.Three coordination polymers are reported: compound 1 exhibit a 2D network with rhombic {Zn4} clusters, while 2 and 3 possess a parallel and a inclined 2D → 3D polycatenated framework, respectively.

•Synthesized three MOFs with novel topology.•Luminescent behavior of complexes 1 and 2 were studied.•The magnetic property of complex 3 was studied.Three novel 3D metal-organic frameworks, {[Zn2(L)(BDC)2]·H2O}n (1), {[Cd2(L)2(BDC)]·(BDC)·7.7(H2O)}n (2), and {[Co(L)(H2O)2]·(BDC)·5(H2O)}n (3) (L = tetrakis(imidazol-1-ylmethyl)methane, H2BDC = 1,4-benzenedicarboxylic acid), have been successfully synthesized by self-assembly of transition-metal salts with a flexible N-containing ligand and 1,4-dicarboxybenzene ligand. Complexes 1–3 have 3D structures with various topologies. In complex 1, the L connects Zn(II) atoms to form 2D layers, which are linked by two kinds of 1D [Zn(BDC)]n chains to generate a 4-connected three-dimensional structure with (6·85)(64·82)(86) topology. In complex 2, Cd(II) atoms are coordinated by L to furnish a 2D layer, and the adjacent layers are linked by BDC ligands as bridging ligands to general a new (4,5)-connected three-dimensional network with a point symbol of (44·62)(44·66). In Complex 3, the L ligands act as 4-connected linkers connecting Co(II) ions to display a 4-connected three-dimensional structure with 4·65 topological net directly. In addition, the solid-state fluorescence, infrared spectra, magnetic property and thermal stability of these complexes have also been investigated.Three novel 3D metal-organic frameworks have been successfully synthesized by self-assembly of transition-metal salts with a flexible N-containing ligand and 1,4-dicarboxybenzene ligand. Complexes 1–3 have 3D structures with various topologies: complex 1 with (6·85)(64·82)(86) topology, complex 2 with a point symbol of (44·62)(44·66), complex 3 with 4·65 topological net directly. The solid-state fluorescence, magnetic property and thermal stability of these complexes have also been investigated.

•A new 3D luminescent Cd(II) metal-organic framework has been obtained and characterized.•It exhibits detection of TNP with high selectivity and recyclability.•It also exhibits quantitative detection of the ultralow temperature.•It can be applied as the first potential dual-functional luminescent sensing material for TNP and temperature.A novel 3D Cd(II) MOF, {[Cd(Ccbp−)(4.4′-bpy)·H2O]·(ClO4−)·2H2O} (1), (Ccbp− = 3-carboxy-1-(4-carboxybenzyl)pyridin-1-ium, 4.4′-bpy = 4.4′-bipyridine), has been successfully synthesized and characterized. Complex 1 possesses a 3D 4-fold interpenetrating dia network with a pyridine cation basic skeleton. This Cd-MOF 1 can be applied as the first potential dual-functional luminescent sensing material for high selective and recyclable sensing of 2,4,6-trinitrophenol and quantitatively detecting the ultralow temperature from 10 to 60 K.A novel luminescent Cd(II) metal-organic framework with 3D 4-fold interpenetrating dia network has been successfully synthesized and characterized. This Cd-MOF 1 can be applied as the first potential dual-functional luminescent sensing material for high selective and recyclable sensing of 2,4,6-trinitrophenol and quantitatively detecting the ultralow temperature from 10 to 60 K.

A Cd(II) coordination polymer (1), {[Cd2(Ccbp)2(dca)Cl·3H2O]·4H2O} Ccbp− = 4-carboxy-1-(3-carboxybenzyl)pyridin-1-ium and dca− = dicyanamide, has been synthesized via a hydrothermal reaction and fully characterized by single-crystal X-ray structural analysis, FTIR spectroscopy, powder X-ray diffraction, and thermogravimetric analysis. Complex 1 has a 2D network structure with uncoordinated functional groups. Its solid-state luminescence properties were measured at room temperature. Complex 1 exhibited a high sensitivity for Fe3+ in DMF solutions of mixed metal ions. In addition, the temperature-dependent luminescence properties of 1 have been investigated and show that the complex acts as a luminescent thermometer over a temperature range from 10 to 90 K.

•Assembly of l- and d-threonine Schiff bases with Zn2 + gave a pair of enantiomers.•Compound 1 exhibits a 1D right-handed helical chain and 2 is left-handed.•Both complexes exhibit 2D homochiral supramolecular structures via hydrogen bonds.•1 and 2 exhibit blue shift behavior and enhanced luminescence phenomenon.Two novel homochiral helical Zn(II) coordination polymers, {[Zn2(nap-l-thr)2(H2O)2]·H2O}n (1) and {[Zn2(nap-d-thr)2(H2O)2]·H2O}n (2) (H2nap-l-thr = N-(2-hydroxy-1-naphthylmethylidene)-l-threonine, H2nap-d-thr = N-(2-hydroxy-1-naphthylmethylidene)-d-threonine) have been successfully synthesized and characterized by elemental analysis, IR, UV–visible and single-crystal X-ray diffraction. It is interesting to note that both complexes are a pair of enantiomers: 1 exhibits 1D right-handed helical chain of [Zn-COO−]∞ and 2 is 1D left-handed helical chain of [Zn-COO−]∞. There are various hydrogen bonds between the adjacent helical chains which result in a 2D homochiral supramolecular layer structure. Notably, under similar synthetic procedure by using the NO3−, CH3COO−, Cl− salts of Zn2 + ion as a starting reagent, and identical compounds were obtained. In addition, the chiral nature of complexes 1 and 2 are confirmed by the results of circular dichroism (CD) spectra measurements. Thermal stability and luminescence properties were also investigated.A pair of enantiomers of Zn(II) coordination polymers have been constructed from l- and d-threonine Schiff bases, and two Zn(II) complexes 1 and 2 exhibit interesting 1D right- and left-handed helical chains, respectively. Both complexes were characterized by X-ray crystallography, PXRD, TGA, CD measurements and luminescence properties.

Six new mixed-ligand coordination polymers, namely, [Zn(1,3-bdc)(3-bpdb)]n (1), {[Zn(1,3-bdc)(4-bpdb)]·2H2O}n (2), [Co(1,4-bdc)(3-bpdb)(H2O)2]n (3), [Ni(1,4-bdc)(3-bpdb)(H2O)]n (4), {[Co5(1,4-ndc)4(3-bpdb)(μ3-OH)2(H2O)2(DMF)2]·2H2O·CH3OH}n (5), and {[Zn2(1,4-ndc)2(3-bpdb)]·H2O}n (6), where 3-bpdb = 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene, 4-bpdb = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene, 1,3-H2bdc = 1,3-benzenedicarboxylic acid, 1,4-H2bdc = 1,4-benzenedicarboxylic acid, and 1,4-H2ndc = 1,4-naphthalenedicarboxylic acid, were synthesized under solvothermal conditions. Single crystal X-ray diffraction analysis revealed that the structures of complexes 1 and 2 were isomorphic and exhibited two-dimensional (2D) double-layered sql nets. Complex 3 had an interesting 2D → three-dimensional (3D) inclined polycatenation net based on 44-sql subunits. Complex 4 featured an uncommon 3D 2-fold cds network, while complex 5 possessed a rare uninodal self-penetrating 10-connected pentacobalt-cluster-based ile-(36.434.53.62) framework. Complex 6 displayed a 2-fold interpenetrated 3D six-connected pcu topology. These different intriguing architectures indicated that the coordination behaviors of metal ions and the coordination modes, the position isomers of carboxylate, and different steric hindrances of aromatics played important roles in the construction of CPs; moreover, bpdb ligands with conformational freedom may affect the formation of the final architectures. The photoluminescence properties of 1, 2, and 6 in the solid state and the magnetic properties of 5 were studied. Moreover, thermal analysis, powder X-ray diffraction, infrared spectroscopy, and elemental analysis were also performed.

•Two rare 2D layered Co(II) amino acid Schiff base complexes were synthesized.•Both the frameworks consist of 1D left- and right-handed helical chains.•Magnetic studies reveal the dominant antiferromagnetic exchange interactions.Two layered Co(II) amino acid Schiff base complexes, [Co(napala)(tbpe)0.5]n (1) and [Co(napgly)(tbpe)0.5]n (2) [H2napala = N-(2-hydroxy-1-naphthylmethylidene)-d/l-alanine, H2napgly = N-(2-hydroxy-1-naphthylmethylidene)-glycine and tbpe = trans-1,2-bis(4-pyridyl)ethylene], have been synthesized by solvothermal methods and characterized using single-crystal X-ray diffraction. The bridging of Schiff base ligands napala2 − or napgly2 − with Co(II) forms one-dimensional (1D) left- and right-handed helical chains which are further pillared by tbpe to build a two-dimensional (2D) grid-based hcb-type framework. Moreover, both complexes show high thermal stability and exhibit antiferromagnetic coupling between the Co(II) centers mediated by the syn–anti-COO−-bridges.Two new Co(II) amino acid Schiff base complexes exhibit 2D grid-based layers. The 2D structures contain left- and right-handed helical chains and trans-1,2-bis(4-pyridyl)ethylene bridges. The magnetic properties of the complexes were studied in details.

•We synthesized a highly selective and sensitive colorimetric signal-responding anion-sensor 1.•The solution of 1 changed from yellow color to red for F−, to orange for AcO− and to brown for OH−.•The color changes of F− are attributed to the deprotonation of the hydroxyl moiety in the binding group.•The commonly competing ions induced none or relatively negligible optical perturbations in the UV–Vis spectral analyses.A highly selective and sensitive colorimetric signal-responding anion-sensor 1, based on 1,8-naphthalimide, was prepared and spectroscopically characterized. Strong visible colorimetric changes in 1 were observed only in the presence of fluoride (yellow-to-red color change), acetate (yellow-to-orange color change) and hydroxyl (yellow-to-brown color change) anions in DMSO. In the UV–Vis spectroscopy titration of F−, two different processes were observed as the concentration of F− increased. In the lower concentration of F−, hydrogen-bond interactions were formed in the first process. The second process of the spectral changes, in the higher concentration of F−, was attributed to the deprotonation of the hydroxyl moiety in the binding group, which was associated with the enhancement in the push-pull effect of the internal charge-transfer transition. The commonly competing Cl−, Br−, I−, ClO4−, PF6−, HSO4− and H2PO4− ions induced none or relatively negligible optical perturbations in the UV–Vis spectral analyses. The present naked-eye detection system provides a simple and rapid method for the detection of fluoride, acetate and hydroxyl anions without interferences from other halide anions or common anions, including ClO4−, PF6−, HSO4− and H2PO4−.

The assembly of Co(NO3)2·6H2O and achiral isonicotinic acid (HIN) under solvo(hydro)thermal conditions yields a three-dimensional chiral Co-based MOF, {[Co6(μ3-OH)2(IN)4(HCOO)6]·4DMF·5H2O}n (1). Polymer 1 consists of a reinforced sinusoidal-like hydroxyl–formate–carboxylate mixed-bridged chain as a rod-shaped secondary building unit (SBU), which is constructed from two types of asymmetric triangular Co3 clusters. This compound also has open irregular channels in the framework and presents a severely distorted pcu net based on two different Co3 clusters of SBUs as six connected nodes. The presence of a few drops of water in the DMF reaction solution is important in in situ HCOO− generation, which is beneficial for the formation of 1. Compound 1 is further characterized by IR, EA, PXRD, TGA-DSC, N2 adsorption, and magnetic measurement.

A 1,8-naphthalimide derivative (1) was intentionally designed and synthesized as a new turn-on fluorescent probe for the detection of zinc ion with high selectivity over other metal ions at pH 7.4 in aqueous media (CH3CN/HEPES, V/V = 6:4). The reaction mechanism is attributed to the replacement of the protons of the O–H groups by zinc ion at the binding site and production of fluorescence which is blocked in the photo-induced electron transfer (PET) process. Remarkable enhancement of up to 13-fold in fluorescence intensity with a 38 nm red-shift was achieved in the detection of zinc ion. Compound 1 was successfully applied to the fluorescence imaging of zinc ion, with a fluorescence emission color produced in the cell nucleus different from that produced in the cytoplasm, in A549, BEAS-2B, CHO, Hela, and HepG2 cells. Furthermore, cytokinesis-block micronucleus (CBMN) assay was carried out in CHO cells using 1 and zinc ion as the imaging agents, showing that the 1-Zn2+ agent is a nucleic acid selective stain, which could be applied in MN assays in different kinds of cell lines.A 1,8-naphthalimide derivative (1) was intentionally designed and synthesized as a new turn-on fluorescent probe for the detection of zinc ion in aqueous media (CH3CN/HEPES, V/V = 6:4). Remarkable enhancement of up to 13-fold in fluorescence intensity with a 38 nm red-shift was achieved in the detection of zinc ion. Compound 1 was successfully applied to the fluorescence imaging of zinc ion, with a fluorescence emission color produced in the cell nucleus different from that produced in the cytoplasm, in A549, BEAS-2B, CHO, Hela, and HepG2 cells. Furthermore, cytokinesis-block micronucleus (CBMN) assay was carried out in CHO cells using 1 and zinc ion as the imaging agents, showing that the 1-Zn2+ agent is a nucleic acid selective stain, which could be applied in MN assays in different kinds of cell lines.

Two novel bpy-bridged CoII Schiff base complexes have been synthesized by the hydro(solvo)thermal reactions of corresponding amino-acid-based Schiff bases, bpy and Co(NO3)2·6H2O. The following formulae identify the two complexes: {[Co(napala)(bpy)0.5]·H2O}n (1) and [Co(napgly)(bpy)0.5]n (2) [H2napala = N-(2-hydroxy-1-naphthylmethylidene)-D/L-alanine, H2napgly = N-(2-hydroxy-1-naphthylmethylidene)-glycine and bpy = 4,4′-bipyridine]. These two compounds have been characterized using single-crystal X-ray diffraction, infrared, powder X-ray diffraction, thermogravimetric analysis, optical spectra analysis, and magnetic measurement. Complex 1 features an unprecedented threefold interpenetrated diamond network based on the fan-shaped CoII4(μ2-napala)4 molecular square node and bpy linker, which represents the first example of 3D framework among the amino-acid-based Schiff base complexes with salicylaldehyde or its derivatives. In 2, adjacent CoII ions are bridged by μ2-napgly2− to form left- and right-handed [CoII(μ2-napgly)]n helical chains. These two types of helical chains are sustained alternately by a symmetrical bpy co-ligand into a 2D grid-based layer. The solid-state fluorescence of complexes 1 and 2 are quenched almost completely compared with free mixed-ligands at room temperature. Moreover, magnetic studies show the dominant antiferromagnetic coupling between the CoII centers mediated by the syn–anti-COO−-bridges in both complexes.

A novel cobalt(II) complex of [Co(4-MePhCOO)2(NITpPy)2(H2O)2] (1), where NITpPy is short for 2-(4-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxy 3-oxide(C12H16N3O2), was synthesized and structurally characterized by X-ray diffraction analysis. The X-ray diffraction analysis reveals that 1 crystallizes in the triclinic space group P-1 with a = 6.7910(10) Å, b = 12.4421(15) Å, c = 12.9169(16) Å, α = 89.8470(10)°, β = 89.8480(10)°, γ = 76.991(2)°, and Z = 1. The Co atom in the complex is located on the center of inversion and lies in a distorted octahedral geometry defined by an N2O4 donor set. The interaction of 1 with calf thymus DNA (CT-DNA) was investigated by UV–vis absorption and emission spectroscopy, which indicating that 1 could bind to DNA through electrostatic interaction.

Cu(II) polymers of Hbidc (1H-benzimidazole-5,6-dicarboxylate), namely [Cu2(Hbidc)2(H2O)4·3H2O]n (1) and [Cu(Hbidc)]n (2), were synthesized under hydrothermal conditions by variation of the reaction temperature and characterized by physico-chemical, spectroscopic and single-crystal X-ray diffraction studies. At temperatures from 100 to 170 °C, we only obtained the 2-D structure compounds 1 and 2, in which the bridging mode of the Hbidc ligand increases from μ3 to μ5 and the number of water ligands decreases to 0. Both compounds have 3-D supramolecular architectures extended by hydrogen bonding and π–π interactions between the adjacent layers. Magnetic studies revealed that compound 1 shows weak antiferromagnetic properties and compound 2 exhibits ferromagnetic coupling between the two Cu(II) ions in the dimeric units.

A one-dimensional chain compound was formed by copper (II) hexafluoroacetylacetonate (hfac) and nitroxide radical 2-(4-pyridyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-oxide (NITpPy). The product was structurally characterized by single crystal X-ray diffraction. [Cu2(hfac)4NITpPy]n crystallizes in the monoclinic C2/c space group with a = 19.70(2), b = 16.834(19), c = 15.274(18) Å, β = 119.073, V = 4427(9) Å3, Z = 4, R = 0.0699 wR2 (all data) = 0.1752. In the compound, two different Cu(hfac)2 units are bridged by NITpPy. The nitrogen atom of pyridine ring is coordinated with Cu(II) ion to afford a three-spin complex. Cu(II) ions of Cu(hfac)2 and the oxygen atoms of nitronyl nitroxide formed weak coordination bonds with the bond length 2.495(8) Å.

The two title compounds were prepared from the ligand pydc with cobalt(II) acetate in the presence of L1 and L2 (L1 = 1,3-bis(4-pyridyl)propane, L2 = 3-amino-1H-1,2,4-triazole, pydc = 2,6-pyridinedicarboxylic acid). The complexes were characterized by elemental analysis, IR spectrum and single crystal X-ray diffraction. Single crystal analysis shows that in two complexes coordination number around Co atom is six with distorted octahedral geometry, and both two complexes consist of ion pairs containing cationic [Co(H2O)n]2+ and anionic [Co(pydc)2]2- units.

•A series of zwitterionic isostructural lanthanide coordination polymers have been obtained.•Complex 1 can serve as the first example of a zwitterionic Ln-CP for selective and recyclable sensing of TNP.•Complex 3 has antiferromagnetic property and exhibits slow magnetic relaxation.A series of isostructural lanthanide coordination polymers (Ln-CPs) {[Ln(Cbdcp)·3H2O]·Cl·xH2O} Ln = Tb (1), Eu (2), Dy (3), Cbdcp = N-(4-carboxybenzyl)-(3,5-dicarboxyl)pyridinium, have been successfully synthesized and fully characterized. Complex 1 utilized as a representative chemosensor has the potential to serve as the first example of a luminescent Ln-CP material based on the zwitterionic type of organic ligand for selective and recyclable sensing of TNP in ethanol solution. Besides, Complex 3 has antiferromagnetic property and exhibits slow magnetic relaxation.A series of isostructural lanthanide coordination polymers based on the zwitterionic type of organic ligand has been successfully synthesized to explore luminescent and magnetic properties. Complex 1 has the potential to serve as the first example of a luminescent zwitterionic Ln-CP material for selective and recyclable sensing of TNP in ethanol solution. Besides, Complex 3 has antiferromagnetic property and exhibits slow magnetic relaxation.

Two novel bpy-bridged CoII Schiff base complexes have been synthesized by the hydro(solvo)thermal reactions of corresponding amino-acid-based Schiff bases, bpy and Co(NO3)2·6H2O. The following formulae identify the two complexes: {[Co(napala)(bpy)0.5]·H2O}n (1) and [Co(napgly)(bpy)0.5]n (2) [H2napala = N-(2-hydroxy-1-naphthylmethylidene)-D/L-alanine, H2napgly = N-(2-hydroxy-1-naphthylmethylidene)-glycine and bpy = 4,4′-bipyridine]. These two compounds have been characterized using single-crystal X-ray diffraction, infrared, powder X-ray diffraction, thermogravimetric analysis, optical spectra analysis, and magnetic measurement. Complex 1 features an unprecedented threefold interpenetrated diamond network based on the fan-shaped CoII4(μ2-napala)4 molecular square node and bpy linker, which represents the first example of 3D framework among the amino-acid-based Schiff base complexes with salicylaldehyde or its derivatives. In 2, adjacent CoII ions are bridged by μ2-napgly2− to form left- and right-handed [CoII(μ2-napgly)]n helical chains. These two types of helical chains are sustained alternately by a symmetrical bpy co-ligand into a 2D grid-based layer. The solid-state fluorescence of complexes 1 and 2 are quenched almost completely compared with free mixed-ligands at room temperature. Moreover, magnetic studies show the dominant antiferromagnetic coupling between the CoII centers mediated by the syn–anti-COO−-bridges in both complexes.