Hydrothermal reactions of rare earth (Nd, Sm, Eu, and Tb) and l- or d-lactic acid are used to construct four pairs of homochiral metal–organic frameworks (HMOFs) with polymetallic building blocks, namely, {[Nd2(L)2(H2O)3]·4H2O}n (1-r)/(1-s) and {[Ln2(L)2(H2O)2]·4H2O}n {Ln = Sm (2), Eu (3), Tb (4)} (n-r)/(n-s). The eight complexes were characterized by single-crystal X-ray diffraction, infrared spectra, elemental analysis, thermogravimetric analysis, electronic circular dichroism (ECD) spectra, and powder X-ray diffraction measurements. The complexes 1–4 featuring a 3D porous metal–organic framework crystallize in chiral space groups, and their chirality is proven by the solid-state ECD spectra. Moreover, the second-harmonic generation (SHG) investigation reveals that the complexes 1-r, 2-r, 3-r, and 4-r have medium SHG eficiencies. The complexes 2, 3, and 4 exhibit relatively high luminescence properties, which could be ascribed to ligand-centered emission. The luminescence of complex 4-r could be quenched by nitrobenzaldehyde, which may be used for molecular sensing and recognition.

Three isomorphic chiral coordination polymers, namely, [M(cpca)·(H2O)]2·H2O (M = Zn (1), Cd (2), and Co (3)), based on a new homochiral dicarboxylic acid ligand, have been synthesized under hydro(solvo)thermal conditions and characterized by single X-ray diffractions, elemental analyses, infrared spectra, thermogravimetric analysis, powder X-ray diffractions, and circular dichroism spectroscopy. The three compounds featured two-dimensional layer structures with one-dimensional pseudo-nanotubes connected together by weak intermolecular interactions, exhibiting a new topological structure with a point symbol of (43·62·8). The influence of ionic radii in tuning the pore size of the coordination polymers is discussed. Furthermore, second harmonic generation (SHG) activity, luminescence and sensing, and asymmetric catalytic properties of all these three chiral coordination polymers have also been studied. All the three complexes show different SHG activities. The luminescence of the complexes could be quenched by nitrobenzaldehyde, which may be used for molecular sensing and recognizing. The three complexes also demonstrate asymmetric catalysis activities toward Henry reactions of nitroaldehyde.

Two novel POMOFs, [Cu4(1,3-dtzb)4(SiW12O40)]n (1) and [Cu4(1,4-dtzb)4(SiW12O40)]n (2), based on Keggin-type polyoxometalates have been hydrothermally synthesized by altering organic ligands {1,n-di(4H-1,2,4-triazol-4-yl)benzene: n = 3 (1,3-dtzb) and 4 (1,4-dtzb)}. In POMOF 1 constructed from the V-shaped 1,3-dtzb meta-ligand, the ligands link the Cu(I) ions to form a 20-member metallomacrocycle with [Cu2(1,3-dtzb)2] as the SBU, four of which assemble into a cage-like [Cu2(1,3-dtzb)2]4 motif to embed the POM anion, resulting in a 3D POMOF showing a new type of topological structure with a point symbol of {4·53·72}{52·8}. However, when the ligand is changed to the 1,4-dtzb straight para-ligand, POMOF 2 with a different structure is achieved. The ligands link the Cu(I) ions into a basic 3,3-connected net, and then the POM anions insert into the space between two adjacent nets to form a POM-pillared double-layer framework. The large cavities of the POM-pillared double layers allow the occurrence of an interpenetrated 2D→3D framework. The cyclic voltammetric behavior and photocatalytic properties of POMOFs 1 and 2 were also investigated.

To investigate the coordination nature of the pyridyl-N-oxide phosphonate ligands with rare earth metals, two series of nine lanthanide complexes, namely, {[Ln(HL)((C2O4)0.5)2(H2O)]·3H2O}n {Ln = Eu(1), Gd(2), Tb(3), Dy(4) and Ho(5)} and {[Ln2(L)(C2O4)2(H2O)3]·H2O}n {Ln = Er(6), Tm(7), Yb(8) and Lu(9)} {H2L = 2-(pyridyl-N-oxide)methylphosphonic acid; H2C2O4 = oxalic acid }, have been hydrothermally synthesized and characterized by IR spectroscopy, thermogravimetric analysis, and powder and single-crystal X-ray diffraction. Complexes 1–5 are isomorphic, featuring a three-dimensional (3D) porous structure with a dia topological framework, while the isomorphic complexes 6–9 show a 3D 3,4-connected topological framework with a point symbol of {72·8}2{73·83}. Photoluminescence spectra of complexes 1 and 3 exhibit the strong luminescence characteristic of Eu(III) and Tb(III) ions, respectively, suggesting that HL− and L2− anions are able to efficiently sensitize the luminescence of lanthanide ions. The magnetic analyses of complexes 2–5 show the characteristic magnetic susceptibilities of isolated Gd(III), Tb(III), Dy(III) and Ho(III) ions, respectively.

Cuprous iodide (CuI)-based coordination compounds with the general chemical formula of CuI(L) are well-known for their structural diversity and strong photoluminescence and are therefore considered as promising candidates for a number of optical applications. Reported here are two cuprous iodide coordination polymers (CPs), {[Cu3I2TBA]·H2O}n (1) and {[Cu2I(HTBA)TBA]·2H2O}n (2) (HTBA = 4-(4H-1,2,4-triazol-4-yl)benzoic acid). Structures of CPs 1 and 2 are determined by single crystal X-ray diffraction and further characterized by infrared spectra (IR), elemental analyses, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. CPs 1 and 2 with a significant feature of novel cationic [(CuxIy)x−y]n motifs are synthesized under controlled reaction conditions via adopting HTBA as ligand. CP 1 displays a 3,6-connected net, while CP 2 shows a coordination chain. Further, the catalytic properties of CPs 1 and 2 are investigated in the degradation of methyl blue.

To investigate the construction of novel chiral coordination polymers and the effect of different substituents on the ligands, three complexes, namely [Co(L)(bimb)]·EtOH·H2O [bimb = 4,4′-bis((1H-imidazol-1-yl)methyl)-biphenyl, L = (R)-4-(4-(1-carboxyethoxy)phenoxy)-3-fluorobenzoic acid (1); L = (R)-4-(4-(1-carboxyethoxy)phenoxy)-3-chlorobenzoic acid (2); L = (R)-4-(4-(1-carboxyethoxy)phenoxy)-3-nitroaniline acid (3)], have been hydrothermally synthesized and characterized by IR, elemental analyses, thermogravimetric analysis, solid state circular dichroism (CD), powder and single-crystal X-ray diffractions. Structure analysis indicates that complexes 1–3 are isomorphic, featuring two-dimensional (2D) 2-fold interpenetrated sq1 structures. In addition, their second harmonic generation efficiency and catalytic activity for the aldol reaction were investigated.A series of chiral coordination polymers exhibit second harmonic generation (SHG) efficiency and asymmetrical catalytic properties toward aldol reactions.

To investigate the synthesis and structure of pyridyl-N-oxide phosphonate ligand based lanthanide complexes, a series of four complexes, namely, [NaLn2(pmpa)(C2O4)2.5(H2O)4]·2H2O {Ln = Sm (1), Eu (2), Gd (3), and Tb (4); H2pmpa = 2-(pyridyl-N-oxide)methylphosphonic acid; H2C2O4 = oxalic acid}, were hydrothermally synthesized and characterized by elemental analyses, FT-IR, powder and single-crystal X ray diffraction analyses, and thermogravimetric analyses. In the preparation of complexes 1–4, the pH value of reaction system exhibited a significant impact on the product structures. Complexes 1–4, which are isomorphic, exhibited Na ions involving a three-dimensional 4-nodal topological framework with the point symbol of {42·52·62·73·8}{42·5}{43·5·62}{43·5·63·73}. This framework can be further simplified to a 2-nodal topology with the point symbol of {318·436·533·64}{33}2. Photoluminescence studies of complexes 1, 2 and 4 exhibited characteristic luminescence of Sm(III), Eu(III), and Tb(III) ions, while complex 3 exhibited a Gd(III) ions disturbed ligand emissions.Four Na-involving lanthanide phosphonate complexes, featuring new 3D topological frameworks and luminescence, were constructed by pyridyl-N-oxide phosphonate ligand.

•Self-assembly of oxomolybdate and 3,5-di(4H-1,2,4-triazol-4-yl)benzoic acid results in [(Mo2O6)L]·CH3OH·3H2O (1).•Complex 1 exhibits an unreported 3D topological structure with a point symbol of (32;42;53;62;7)2(32;83;9).•Luminescent analysis of 1 reveals that the MoVI ions are able to tune the luminescent emission of the L ligand.•The electrochemical analysis shows that the work electrode of 1 exhibits a surface-controlled redox process.A new complex namely, [(Mo2O6)L]·CH3OH·3H2O (1), based on oxomolybdate and 3,5-di(4H-1,2,4-triazol-4-yl)benzoic acid (L) was synthesized under hydrothermal condition, which shows a new three-dimensional supramolecular framework with unreported topological structure. In addition, the luminescent and electrochemical behaviors of complex 1 were investigated.A triazole-MoIV complex is hydrothermally synthesized with interesting 3D supramolecular framework with unreported topological structure and fluorescence and electrochemical properties.

•Six new pyrimidine derivatives complexes show 3D H-bonding supramolecular structures.•They show catalytic activities on the photocatalytic degradation of methyl blue.•They show catalytic activities on the oxidation of benzyl alcohol.•Complex 5 shows antitumor activity against HepG2 cells growth.Six pyrimidine derivatives based coordination complexes, namely, [Co(mpd)2(H2O)4]·2H2O (1), [Ni(mpd)2(H2O)4]·2H2O (2), [Co(hta)(H2O)3]·H2O (3), [Ni(hta)(H2O)3]·H2O (4), [Cu(Hhta)2(H2O)2]·3H2O (5) and [Zn(hta)(bpy)2]·2H2O (6) (Hmpd = 7-methylimidazo[1,2-a]- pyrimidine-2,5(1H,3H)-dione; H2hta = 2-(4-hydroxy-6-methylpyrimidin-2-ylthio) acetic acid; bpy = 4,4′-bipyridine) have been synthesized and characterized by elemental analysis, IR spectroscopy, PXRD, thermogravimetric analyses and X-ray crystallography. In the packing structures of the complexes, the hydrogen bonds (H-bonds) play important roles. The isomorphic complexes 1 and 2 show 3D tfz-d topology based on twelve H-bonds. Complex 3 and 4 are also isomorphic, exhibiting an unreported H-bonding 3D topology with 8H-bonds in the packing structure respectively. Complex 5 with fourteen H-bonds presents a H-bonding 3D new topology. {(H2O)4O2} H-bonding clusters in complex 6 link the coordination chains into a H-bonding 3D rtw topology. In addition, the catalytic properties of complex 1–6 are investigated. Compared with the other complexes, complex 5 exhibits the best catalytic performance in the decolorization of methyl blue (MB) and the oxidation of benzyl alcohol to benzaldehyde. Meanwhile, complex 5 also shows antitumor activity against HepG2 cells growth with an inhibition rate of 50.1%.Six pyrimidine derivatives based coordination complexes are synthesized which all show hydrogen bonding supramolecular structures, and the catalytic and anticancer activities of them are investigated.

Reactions of 5-(4-nitrophenyl)-1H-tetrazole (H(4-nptz)) and 5-(4-nitrobenzyl)-1H-tetrazole (H(4-nbtz)) with transition metals under solvothermal conditions yield two new coordination polymers, namely, [CuI(4-nptz)(CH3CN)]n (1) and [Zn(4-nbtz)2]n (2). Both of them were characterized by IR, thermogravimetric analysis, X-ray crystallography. Single crystal X-ray diffraction analysis reveals that 1 is of three-dimensional (3D) sqc184 type supramolecular framework, while 2 is of 3D sqc1 type supramolecular framework. In addition, solid state UV–Vis diffuse reflectance and photoluminescence properties of 1 and 2 are investigated. Furthermore, the catalytic properties for the coupling reaction of α-amino acids and bromobenzene were also investigated.Two tetrazolate derivatives based coordination polymers are synthesized which both show three-dimensional hydrogen bonding supramolecular frameworks, and the property of them to catalyze the coupling reaction of α-amino acids and bromobenzene was also investigated.