Vol 42, No 7 (2016)

Two new porous coordination polymers based on cluster anions [Re₄Te₄(CN)₁₂]^4– and cationic Ln³⁺ (Ln = La, Gd) complexes with 1,10-phenanthroline (Рhen) are synthesized under hydrothermal conditions. The structures of the compounds are determined by X-ray diffraction analysis (CIF files CCDC 1437445 (I) and 1437446 (II)). Compound (РhenH)[{La(H₂O)₃(Рhen)₂}{Re₄Te₄(CN)₁₂}] · 1.5Рhen · 6H₂O (I) crystallizes in the space group \(P\bar 1\) (triclinic system): a = 13.322(3), b = 15.977(3), c = 18.576(4) Å, α = 71.34(3)°, β = 85.56(3)°, γ = 88.27(3)°, V = 3734.8(13) ų. Compound (PhenH)[{Gd(H₂O)₂(Phen)₂}{Re₄Te₄(CN)₁₂}] · 2Phen · 0.5H₂O (II) crystallizes in the space group C2/c (monoclinic crystal system): a = 18.146(1), b = 30.245(2), c = 13.455(2) Å, β = 97.858(2)°, V = 7315.4(1) ų. Structures I and II are based on polymer chains consisting of alternating fragments [Re₄Te₄(CN)₁₂]^4– and {Ln(H₂O)_n(Phen)₂}³⁺ (Ln = La, n = 3; Ln = Gd, n = 2) linked by the bridging CN ligands. The packings of the polymers contain extended channels due to the developed network of noncovalent interactions. The walls of the channels are formed by both hydrophilic (CN^–) and hydrophobic (Рhen) groups. The channels, whose volume is 25 and 15% for compounds I and II, respectively, are filled by disordered Phen molecules and PhenH⁺ cations, as well as by H₂O molecules.

Reaction of tridentate Schiff bases with nickel and cadmium salts in methanol afforded two new mononuclear complexes, [Ni(L¹)₂] (I) and [Cd(L²)₂] (II), where L¹ and L² are the anions of 2-bromo-4-chloro-6-[(3-dimethylaminopropylimino)methyl]phenol (HL¹) and 2-bromo-4-chloro-6-[(3-morpholin-4-ylpropylimino)methyl]phenol (HL²), respectively. The complexes were characterized by singlecrystal X-ray diffraction (CIF files CCDC nos. 1428653 (I) and 1428654 for (II)), FT-IR, and elemental analysis. Complex I crystallizes in the monoclinic space group P2₁/c, with a = 8.8216(8), b = 14.0424(8), c = 11.8687(12) Å, β = 111.238(2)°, V = 1370.4(2) ų, Z = 2. Complex II crystallizes in the monoclinic space group P2₁/n, with a = 9.6774(4), b = 15.8970(6), c = 20.3144(7) Å, β = 90.408(2)°, V = 3125.1(2) ų, Z = 4. The metal atoms in the complexes are coordinated by two tridentate Schiff base ligands, forming octahedral coordination. The free Schiff bases and the complexes were assayed for antibacterial activities. Both complexes are more active against the bacteria than the free Schiff bases. Complex II has the MIC value of 0.39 μg mL^–1 against Bacillus subtilis.

Tetra(para-tolyl)antimony aroxides, [(4-MeC₆H₄)₄SbOC₆H₃Cl₂-2,6] • 1/2TolH (IА, IВ), (4-MeC₆H₄)₄SbOC₆H₃(NO₂)₂-2,4 (II), and (4-MeC₆H₄)₄SbOC₆H₂(NO₂)₃-2,4,6 (III), are synthesized by the reactions of penta-para-tolylantimony with 2,6-dichlorophenol, 2,4-dinitrophenol, and 2,4,6-trinitrophenol, respectively, in toluene. The structures of the synthesized compounds are determined by X-ray diffraction analysis (CIF files CCDC 1050584 (I), 1433797 (II), and 999305 (III)). The Sb atoms in compounds IА, IВ, and II have a distorted trigonal bipyramidal coordination with the aroxy groups in the axial positions (axial angles CSbO are 178.01(6)°, 177.74(7)°, and 174.42(11)° and Sb–O angles are 2.244(1), 2.230(2), and 2.507(3) Å). In crystal III, the CSbC angles in the tetrahedral cation [(4-MeC₆H₄)₄Sb]⁺ are 103.6(2)°–116.22(2)°. A weak interaction is observed between the cation and picrate anion [OC₆H₂(NO₂)₃-2,4,6]^–(Sb···O distance is 3.472(3) Å).

The reaction of different macrocyclic metallic tectons and dicarboxylic acid ligand yielded six new coordination polymers, namely, {[(NiL¹)(4,4'-Bpdc)] • DMF • 2.5H₂O}_n (I), {[(NiL²)(4,4'-Bpdc)] • DMF • 2.5H₂O}_n (II), [(NiL³)₂(4,4'-Bpdc)_1.5][(NiL³)(4,4'-Bpdc)] • ClO₄ • 28H₂O (III), {[(NiL⁴)(4,4'-Bpdc)] • 4H₂O}_n (IV), {[(NiL⁵)(4,4'-Tpdc)] • 5H₂O}_n (V), {[(NiL³)(4,4'-Tpdc)]}_n (VI) (L¹ = 1,4,7,9,12,14-hexaaza-tricyclo[12.2.1.1^4.7]octadecane, L² = 1,3,10,12,15,18-hexaazatetracyclo[16.2.1.1^12.15.0^4.9]docosane, L³ = 11-methyl-1,4,8,10,13,15-hexaaza-tricyclo[13.3.1.1^4.8]icosane, L⁴ = 1,3,10,12,16,19-hexaazate-tracyclo[17.3.1.1.^12.16,0^4.9]tetracosane, L⁵ = 1,4,8,10,13,15-hexaaza-tricyclo[13.3.1.1^4.8]icosane, 4,4'-Bpdc = 4,4'-biphenyldicarboxylic acid and 4,4'-Tpdc = 4,4'-terphenyldicarboxylic acid) (CIF files CCDC nos. 1055545–1055550 for I–VI, respectively). Except for the different conformations of the macrocyclic metallic tectons or dicarboxylic acid ligands, complexes I–VI crystallized under the same environment, however, they exhibit diverse packing mode of infinite 1D coordination polymers, showing macrocyle or dicarboxylic acid ligand regulated self-assemble. The solid states UV-Vis for complexes I–VI also have been investigated.

Two nine-coordination coordination polymers of neodymium, [Nd₂(p-C₈H₄O₄)(o-C₈H₄O₄)₂ • 4H₂O]_n (I), [Nd₂(C₁₀H₄O₈)(C₁₀H₂O₈) • 2H₂O]_n (II), have been prepared by hydrothermal reaction of Nd(NO₃)₃ • 6H₂O with terephthalic acid and phthalic acid, or benzenetetracarboxylic anhydride and determined by means of IR, UV, fluorescence, TG-DTA, cyclic voltammetry (CV) and X-ray single-crystal diffraction methods (CIF files CCDC nos. 1006206 (I), 979309 (II)). Yellow-green luminescence could been observed at 391 nm (λ_ex = 305 nm) for complex I and 370 nm (λ_ex = 331 nm) for the complex II. The emission of complexes I and II may be due to the π* → n transition, which may be assigned to the ligand-to-metal charge-transfer bands. Compared with complex II, the complex I exhibits a stronger fluorescence intensity for the different coordinated environment. Cyclic voltammetric measurement of the two compounds reveal that the compounds both have a couple of irreversible redox peak, indicating that the two polymers were both corresponded to the unusual Nd(III)/Nd(V).