Solvothermal reaction of lanthanide(Ⅲ) salts with fluorescein (2-(6-hydroxy3-oxo-3H-xanthen-9-yl)benzoic acid) led to a series of new coordination polymers {[Ln(C 20 H 11 O 5)(C 20 H 10 O 5)(H 2 O)]·DMF} n (Ln=Er,Eu,Gd,Tb,Tm,Yb).The PXRD patterns of the complexes indicate they are isomorphous.The structure of complex {[Er(C 20 H 11 O 5)(C 20 H 10 O 5)(H 2 O)]·DMF} n has been determined by single-crystal X-ray diffraction,revealing a 2D framework in which DMF molecules were filled between the layers.The crystal structure belongs to the triclinic system,space group P1,with a=12.107(4),b=12.232(4),c=13.273(4),α=68.005(7),β=88.024(11),γ=77.451(8)°,V=1776.7(9) 3,Z=2,D c=1.720 g/cm 3,μ=2.434 mm-1,F(000)=918,R int=0.0584,T=293(2) K,the final R=0.0621 and wR=0.1501.
A new quaternary rare-earth sulfide,Cs0.75(6)Er4.43(5)In3.32(6)S12(1),is discovered by high temperature solid state reactions with a slight excess of CsCl flux.The structure is characterized by single-crystal X-ray diffraction data,while crystallizes in hexagonal space group P63/m(No.176)with a=12.0329(6),c=3.8693(5),V=485.18(7)3,Z=1,Mr=1606.57,Dc=5.499 g/cm3,μ=25.457 mm-1,F(000)=752,the final R=0.0337 and wR=0.0904 for 328observed reflections with I>2σ(I).Its structure features a three-dimensional framework with hexagonal channels that are centered by Cs cations.Such channels are formed by double chains of edge-sharing M(1)S6(M(1)=Er(1)/In(1))octahedra and single chains of Er(2)S6triprism interconnected by corner-sharing.The syntheses,single-crystal analyses,optical band gap and magnetic property are reported.
Treatment of resorcin[4]arene tetracarboxylic acid 1 with triethylamine in the presence of Co(CH3COO)2·4H2O and 4,4'-bipyridine gave a co-crystallization 14-·4Et3NH+(C32H20O164-·4Et3NH+,Mr=1069.27) from ethanol and water.The compound was structurally determined by single-crystal X-ray diffraction.The crystal belongs to monoclinic,space group P21/n,with a=8.1763(18),b=12.913(3),c=28.724(7) ,β=97.574(4)o,V=3006.3(12) 3,Z=2,Dc=1.181 g/cm3,F(000)=1152,Rint=0.0275,T=293(2) K,μ=0.086 mm-1,the final R=0.0634 and wR=0.1752 for 5082 observed reflections with Ⅰ > 2σ(Ⅰ).The co-crystallization is very stable at room temperature.Possibly,a network of N-H···O(=C) plays an important role in the structure.Meanwhile,the compound emits a weak cyan luminescence with peak maximum band at 458 nm.
Three new cadmium or zinc arenedisulfonate complexes [Zn(bpp)2(L)]n 1, {[Cd(bpp)2(1,5-NDS)(H2O)2]·4H2O}n 2 and {[Cd(bpp)2(H2O)2]·(1,5-NDS)}n 3 (L = 4,4'-bis(2-sulfo- natostyryl)biphenyl, bpp = 1,3-di(4-pyri-dyl)propane and 1,5-NDS = 1,5-Naphthalenedisulfonate) have been synthesized from aqueous solution and structurally characterized by infrared spectroscopy, elemental analysis and single-crystal X-ray diffraction. Crystal data for complex 1: space group P21/n, a = 10.559(3), b = 13.138(4), c = 17.623(5) , β = 100.852(3)o, V = 2400.9(12) 3, Z = 2, Dc = 1.351 g/cm3, F(000) = 1016, μ = 0.654 mm–1, the final R = 0.0412 and wR = 0.0994; Crystal data for complex 2: space group P1, a = 8.5642(19), b = 10.076(3), c = 12.114(3) , α = 81.623(7), β = 77.149(8), γ = 82.787(7)o, V = 1003.6(4) 3, Z = 1, Dc = 1.495 g/cm3, F(000) = 466, μ = 0.713 mm-1, the final R = 0.0241 and wR = 0.0713; Crystal data for complex 3: space group C2/c, a = 21.6024(15), b = 9.4608(5), c = 18.4656(11) , β = 107.359(3)o, V = 3602.0(4) ?3, Z = 4, Dc = 1.533 g/cm3, F(000) = 1704, μ = 0.780 mm–1, the final R = 0.0229 and wR = 0.0572. The X-ray single diffraction reveals that 1 exhibits a 3D metal-organic framework formed from 2D Zn(bpp)22+ networks connected by L in the third dimension; 2 and 3 possess 3D and 2D architectures constructed from 1D polymeric chains through H-bond. Complexes 1～3 display photoluminescent emissions at 452 and 335 nm, respectively.
Two new transition-metal organic coordination polymers [M(mna)2](M = Cd(1),Zn(2);mna = 2-mercaptonicotinic anion) have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction along with IR and elemental analyses.Compound 1 is generally a one-dimensional linear structure bridged through the sulfur donor of mna ligand,while 2 is a one-dimensional zigzag chain ligated via the oxygen donor of mna ligand.These compounds further result in three-dimensional structures via intermolecular π...π stacking interactions and/or hydrogen bonding interactions.The two compounds were structurally determined by single-crystal X-ray diffraction.Complex 1 crystallizes in monoclinic space group P21/c with a = 3.730(3),b = 13.973(12),c = 12.380(11) ,β = 97.953(18)°,V = 639.0(10) 3,Z = 2,CdC12H8O4N2S2,Mr = 420.72,Dc = 2.187 g/cm3,F(000) = 412,Rint = 0.0252,T = 293(2) K,μ = 2.052 mm?1,the final R = 0.0269 and wR = 0.0586 for 1377 observed reflections with I > 2σ(I).Complex 2 belongs to monoclinic space group P21/c with a = 13.376(2),b = 12.8429(14),c = 7.4856(10) ,β = 96.190(10)°,V = 1278.5(3) 3,Z = 4,ZnC12H8O4N2S2,Mr = 373.69,Dc = 1.941 g/cm3,F(000) = 752,Rint = 0.0414,T = 293(2) K,μ = 2.264 mm?1,the final R = 0.0418 and wR = 0.0966 for 2396 observed reflections with I > 2σ(I).
A new tri-nuclear mixed metal thiolate complex [Ag(PPh3)2]2[Ni(edtO2)2] 1 has been synthesized and structurally characterized by single-crystal diffraction.The molecule has a crystallographic inversion centre occupied in the central Ni(II) atom and the two silver(I) atoms are related by the inversion centre.The unique structural feature is that one of thiolates of each edt ligand has been oxidized to sulfinate from the precursor [Ni(edt)2]2-to the neutral linear trinuclear complex.The crystal structure belongs to the monoclinic system,space group P21/n with a = 13.581(11),b = 12.239(9),c = 22.316(17) ,β = 103.08(2)o,V = 3613(5) 3,Z = 2,Mr = 1571.87,Dc = 1.445 g/cm3,μ = 1.046 mm-1,F(000) = 1604,T = 293(2) K,the final R = 0.0652 and wR = 0.1499 for 6776 observed reflections with I > 2σ(I).
In order to explain the opposite phase matchability of two types of newly discovered chalcogenides, AX_2MQ_6 vs AX_4M_5Q_(12) belonging to the same R3 space group, the linear and nonlinear optical properties are calculated. The calculated Electron Localization Function(ELF) show the acentricity of the bonds on the Q^(2-) ions with sp^3 hybridization is the main origin of the optical anisotropy. To quantify such an acentricity, a geometric parameter, the dihedral angle between the tetrahedral undersides and the xy-planes is defined. And the calculated birefringence depends on the above defined geometric parameter and the ion radius. This correlation reasonably explains the opposite phase matchability of two closely related chalcogenide families of AX_2MQ_6 and AX_4M_5Q_(12) and is shedding useful light on further exploration on phase matchable IR-NLO crystals.
The creation of a porous magnet is a long-sought academic goal since magnetism and porosity are hostile to one another. While long-range magnetic ordering needs spin carriers of short separation through short bridges, porosity relies on the use of extended connecting ligands. Here, we will give a survey of the cluster-based magnetic porous coordination polymers, i.e., 0-D MPCPs, according to their functional subunits: (1) nanoporous spin crossover materials with single metal nodes; (2) metal-radical approach with rigid organic radical ligands and single metal nodes; (C) PCPs with rigid organic ligands and metal oligomer nodes; (D) PCPs with metal complex linkers and polymetal cluster nodes; (E) PCPs with organo-polymetal cluster linkers and single metal nodes. The assembly from clusters can provide a reasonable route to resolve the hostility between magnetism and porosity. This assembly’s merits are obvious: the pore benefits from the big cluster according to "Scale Chemistry", and the functional framework inherits interesting physical properties from the clusters with a large ground spin S.
Two manganese complexes, [Mn3(2-cba)6(phen)2] 1 (2-cba = 2-cyanobenzoic acid, phen = 1,10-phenanthroline) and [Mn2(4-fbao)2(phen)4](PF6)2·2H2O 2 (4-fbao = 4-formylbenzoic acid oxime), have been synthesized by the reaction of 2-formylbenzoic acid oxime (2-fbao, H2L1) or 4-formylbenzoic acid oxime (4-fbao, H2L2) with phen and manganese acetate in ethanol or methanol solution. A translation from the oximino (-CHN=OH) of H2L1 to cyano (-C≡N) was found in the formation of complex 1 at room temperature. The complexes were structurally determined by single-crystal X-ray diffraction. The crystal of compound 1 belongs to monoclinic, space group C2/c, with a = 17.983(6), b = 23.364(7), c =14.589(5) , β = 92.401(5)o, V = 6124(3) 3, Z = 4, C72H40Mn3N10O12, Mr = 1401.96, Dc = 1.521 g/cm3, F(000) = 2852.0, Rint = 0.0372, T = 293(2) K, μ = 0.686 mm-1, the final R = 0.0644 and wR = 0.1813 for 5803 observed reflections with I > 2σ(I). The crystal of compound 2 is of monoclinic system, space group P21/n, with a = 13.050(4), b = 20.577(5), c = 13.323(4) , β = 113.578(3)o, V = 3227.2(14) 3, Z = 2, C64H48F12Mn2N10O8P2, Mr = 1484.94, Dc = 1.528 g/cm3, F(000) = 1508.0, Rint = 0.0295, T = 293(2) K, μ = 0.539 mm-1, the final R = 0.0629 and wR = 0.1789 for 5298 observed reflections with I > 2σ(I). Compounds 1 and 2 are linear trinuclear and dinuclear manganese complexes respectively, which are both bridged by carboxylate groups of the ligands.
