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Five new copper(I)/silver(I) complexes containing 2-aminopyridine, [Cu(μ-Cl)(2-Apy)(PPh 3 )] 2 ( 1 ), [Ag(μ-Cl)(2-Apy)(PPh 3 )] 2 ( 2 ), [Ag(μ-Br)(2-Apy)PPh 3 )] 2 ( 3 ), [Ag(μ-ONO 2 )(2-Apy)(PPh 3 )] 2 ( 4 ), [Ag(μ-ONO 2 )(2-Apy)(AsPh 3 )] 2 ( 5) have been synthesised for the first time. Complexes 1 – 5 are obtained by the reactions of MX (MX = CuCl for 1 ; M = Ag for 2–5 ; X = Cl, Br for 2 – 3 ; X = NO 3 for 4–5 ) with the monodentate ligands EPh 3 (E = P for 1 – 4 ; E = As for 5 ) and 2-Apy in the molar ratio of 1:1:2 in the mixed solvent of CH 2 Cl 2 and MeOH. Complexes 1 – 5 are characterised by IR and X-ray diffraction. In 1 – 5, chloride, bromide and nitrate ions bridge two metal atoms to form dinuclear complexes containing the parallelogram cores M 2 X 2 (M = Cu, Ag).

Four new complexes [Cu(H2biim)2(H2O)](NO3)2 (1), [Cu(H2biim)2](ClO4)2·2DMSO (2), [Cu(H2biim)2] [I0.36·(NO3)0.64]2 (3) and {[Cu(H2biim)2(H2O)](SiF6)}·H2O (4) (H2biim = 2,2′-biimdazole, DMSO = dimethyl sulfoxide) have been synthesized and characterized by X-ray diffraction. The different inorganic anions NO 3 - , ClO 4 - , [I0.36·(NO3)0.64]− and SiF 6 2 - in these complexes lead to different 3D structures. Among them, complex 3 has an interesting 3D porous structure with two [I0.36·(NO3)0.64]− ions as guests in the cavity. Compound 4 was obtained by the reaction of Cu(BF4)2 with H2biim in water in glass bottle. The robust hydrogen bond of typeV R21(7) played a key role in the formation of SiF 6 2 - in complex 4.

When the reaction conditions are deliberately controlled by the pH, two different polynuclear manganese complexes, (Δ, Λ)-{Mn3(phen)2 (CH3COO)6} (1) and [Mn(phen)Cl2]n (2) (phen = 1,10-phenanthroline), have been synthesized from the same raw materials. The structural analyses show that 1 has a structure formed by neutral chiral linear trinuclear molecules, while 2 has a structure consisting of one-dimensional infinite chains. A study of the temperature dependent magnetic susceptibilities reveal that 1 is an antiferromagnetically coupled trimer molecule while 2 shows ferromagnetic interactions within the chain.

Three Mn II -terephthalate coordination polymers, {Mn II (tp)(bpy)(H 2 O)} n ( 1 ), { Mn 3 II ( tp ) 6 / 2 ( bpy ) 2 · ( dmf ) } n ( 2 ) and {Mn II (tp)(phen)} n ( 3 ) (tp = terephthalic dianion, bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline) have been synthesized and characterized by single crystal X-ray diffraction studies and low temperature (2–300 K) magnetic measurements. The structure analysis of 1 – 3 show that they all are coordination polymers composed of Mn atoms as nodes and terephthalate dianions as spacers. Interestingly, compound 1 consists of 1D infinite zigzag chains, while compound 2 consists of 2D sheets and compound 3 has a 3D framework structure. The study of the temperature dependent magnetic susceptibilities revealed that all of the polymers show antiferromagnetism.

A novel super-molecular complex [Na(DB18C6)(CH3CN)]3 [α-PW12O40] was obtained by solvothermal reaction and characterized by IR, X-ray, 1H, 13C and 31P NMR. The result reveals that the complex consists of an [α-PW12O40]3− anion with α-Keggin structure and three complex [Na(DB18C6)(CH3OH)]+ cations in which every sodium ion located in the cavity of dibenzo-18-crown-6 with six Na–O bonds and coordinated with one of the terminal O atom of [α-PW12O40]3− and the N atom of CH3CN from two sides of the distorted DB18C6 plane, respectively. The three terminal O atoms linked with sodium ion are from a single W3O3 triplet of the α-Keggin tungstophosphate anion. The 13C resonance (119.27 ppm) bonded to N atom in CH3CN has been clarified by gUMBC spectrum (see Fig. 1 ), which is too weak to be observed in 13C NMR spectrum due to its too low relaxation rate.

The title complexes of [Na(N-(p-Rph)15C5Et2O)]2Na2WxMo8−xO26 [(1) : R = H, x = 0.26 : (2): R = CH3, x = 0.50] were synthesized by the reaction of N-(p-Rph)15-crown-5 with tetra-n-butylammonium polymolybdotungstate and a sodium and characterized by elemental analysis, IR, 1H NMR and H,H-COSY NMR spectra and crystal structure determination of complex (2). The complexes can be described as having a two-dimensional [Na2WxMo8−xO26]∞2− anion framework in which the soddium is coordinated with six termial O atoms of neighbouring β-octamolybdotungstates in octahedral geometry and a [Na(N−(p-Rph)15C5(Et2O)]+ complex cation in which the sodium cation shows pentahedral pyramidal coordination geometry, which is rarely observed. The packing of the complex cations and the two-dimensional anion framework were in different layers separately. The N(para-substituted-phenyl)aza-15-crown-5 combined with the octamolybdotungstate anion with a ratio of W/Mo of 0.26/7.74 in complex (1) and 0.50/7.50 in complex (2), respectively, however the DB18C6 and DB24C8 chose the hexamolydotungstate anion with a ratio of W/Mo of 4/2 and 1/5 to form the complexes [Na(DB18C6) (CH3OH)]2W4Mo2O19 and [Na(DB24C8)]2W1Mo5O19.