三氟乙酸铜与邻菲罗啉配合物的合成

选用三氟乙酸铜的盐溶液,以邻菲罗啉为配体,首次合成了三氟乙酸铜的邻菲罗啉配合物,并选用乙醇/乙酸乙酯混合溶剂,水浴培养得到蓝色块状晶体。利用高斯软件对其可能结构进行了模拟计算,并通过红外表征证实了模拟结果的准确性,确定了合成配合物的结构式为[Cu(C12H8N2)2H2O](CF3COO)2。

一个新型层状化合物[Ni(C_(10)H_8N_2)_2V_3O_(8.5)]的水热合成与晶体结构

A novel layered compound, [Ni(C 10 H 8N 2) 2V 3O 8 5 ], was hydrothermally synthesized and structurally characterized by single crystal X ray diffraction. The compound crystallizes in monoclinic system, space group P2 1/c with a =1 551 8(3) nm, b =1 476 1(3) nm, c =1 048 3(2) nm, β=92 02(3)°, V = 2 399 8 (8) nm 3, Z=4, R=0 046 7, wR 2= 0 085 9.

4, 4′-二羧基二苯基砜的镧系配合物的合成和结构

合成了V型半刚性配体4,4′-二羧基二苯基砜的3个新的镧系配合物[Nd2(dbsf)3(DMF)2.25(H2O)1.75]·1.25DMF·0.5MeOH(1),[Yb2(dbsf)3(H2O)2]·1.5H2O(2)和[Er2(dbsf)3(H2O)2]·0.75H2O(3)(H2dbsf=4,4′-二羧基二苯基砜,DMF=N,N-二甲基甲酰胺,MeOH=甲醇),并测定了它们的晶体结构。结构表明配合物1具有一维孔道的三维镧系金属-有机骨架结构(LnOF),未配位的DMF和MeOH填充在孔道中;配合物2和3也具有三维的LnOF结构,但晶格水存在于洞穴里。它们的形成与结构特征可能与半刚性V型配体H2dbsf和镧系收缩效应有关。

氢键在晶体工程及难溶性药物开发中的应用

氢键在超分子化学、固体材料设计及生物化学(主要是蛋白质的折叠)中扮演了十分重要的角色,强氢键和C-H…O弱氢键对于配合物晶体和药物晶体的形成起到了非常重要的作用。资料表明,零维、一维及许多二维结构构成三维结构是依靠氢键来实现的。同时,在药物开发中,对于含有氢键供体官能团的难溶性药物,可以将药物制备成固体分散体,利用药物与载体材料之间形成氢键相互作用,达到提高药物溶出度及生物利用度的目的。

MnHg(SCN)_4与ZnCd(SCN)_4晶体的晶格振动及热导率的拉曼光谱研究

采用拉曼光谱技术研究了金属有机配合物晶体MnHg(SCN)4(MMTC)和ZnCd(SCN)4(ZCTC)的晶格振动模式.结果表明,MMTC有4类晶格振动模式:SHgS弯曲振动、NMnN弯曲振动、CS弯曲振动和CN伸缩振动;ZCTC有4类晶格振动模式:双重简并CdS4弯曲振动、双重简并ZnN4弯曲振动、SCN弯曲振动和CN伸缩振动.根据晶格动力学理论,推导了晶体热导率及拉曼峰半高宽的关系,计算了上述两种晶体的热导率,讨论了该类晶体激光损伤的物理机制.

酸根阴离子和体系的pH值及对水热条件下晶体生长的影响

目的通过调节[Ni(II)(Dipha)(Benzidine)]体系的pH值和改变L-(L-=Cl-,NO3-),研究其在水热条件下对晶体生长的成晶条件。方法通过水热法合成该体系的系列晶体。结果实验表明,水热法合成该体系的系列晶体,pH≈7.0,镍盐(NiL2)选用NiCl2或Ni(NO3)2有利于配合物晶体的形成。结论对于该体系溶液pH≈7.0和选择合适的酸根阴离子盐来提供金属离子有利于配合物晶体的形成。

Synthesis,crystal structure and photo-physical properties of tris(4-methyl-2,5-diphenylpyridine)iridium for OLED

Organic light-emitting diodes(OLEDs)have important applications in the field of next-generation displays and lighting,and phosphorescent iridium complexes are an important class of electroluminescent phosphorescent materials.In this paper,Ir(bmppy)_(3),tris(4-methyl-2,5-diphenylpyridine)iridium,was synthesized and elvaluted for photo-physical characteristics.Single crystals suitale for X-ray diffraction(XRD)were grown from a mixture solvent of dichloromethane and absolute ethanol.The composition and structur of Ir(bmppy)_(3)were determined by element analysis,NMR spectra and XRD.The complex crystallizes in the monoclinic symmetry with the space group P21/c with a slightly distorted octahedral configuration.As measured by UV-Visible and photoluminescence spectra,Ir(bmppy)_(3) displays a maximum emission at at 527 nm at ambient temperature,a typical green-emitting profile.The complex has potential for application in the OLED industry.

Synthesis, crystal structure and magnetic properties of novel copper compound Cu(phen)(m-CBA)_2

A novel compound Cu（phen）（m-CBA）2 was synthesized with m-chlorobenzoic acid（m-CBA）, 1,10-phenanthroline（phen） and Cu（OAc）2·H2O. It was characterized by IR, UV, elemental analyses and X-ray crystallography. It crystallizes in the monoclinic crystal system with C2/c space group, a=2.9699（4） nm, b=1.15452（2） nm, c=1.5335（2） nm, β=111.118（2）°, V=4.905 1（1） nm3, Z=8, F（000）=2 328, R1=0.072 8, wR2=0.223 4 [I2σ（I）]. Structure analysis shows that the copper center coordinates with two nitrogen atoms from one 1,10-phenanthroline molecule, two oxygen atoms from two m-chlorobenzoic acid molecules, giving a distorted squared planar coordination geometry. This novel compound shows paramagnetic interactions between copper centers.

Synthesis and Structure of anti-Configuration Complex [Cu(tssb)_2]·2[(H_3O)Cl]·4H_2O

The title complex [Cu(tssb)2]2[(H3O)Cl]4H2O (C18H34Cl2CuN2O14S2) (tssb = tau- rine salicylaldehyde Schiff base) has been synthesized by the reaction of taurine salicylaldehyde Schiff base (tssb) and copper acetate in water-ethanol. Its single-crystal structure was determined by X-ray diffraction method. The crystal structure belongs to triclinic, space group P1 with a = 0.7407(1), b = 1.3329(3), c = 1.5736(3) nm, ?= 103.800(4), ?= 95.030(4), ?= 104.416(4)? Mr = 701.06, V = 1.4433(5) nm3, Z = 2, Dc = 1.613 g/cm3, = 1.153 mm-1 and F(000) = 726. The compound is an infinitely expanding three-dimensional network connected with hydrogen bonds. The Cu(Ⅱ) atom is coordinated by two nitrogen and two oxygen atoms to form a distorted planar coordination compound which adopts anti-configuration because two sulfonic acid groups are posi- tioned diagonally on a plane.

Synthesis and Characterization of a Two-dimensional Cadmium(II) Compound Involving Covalent and Hydrogen Bonds

A two-dimensional hydrogen-bonded cadmium(II) compound [Cd(dapm)2- (CH3COO)2(H2O)2] (dapm = diaminodiphenylmethane) has been synthesized and characterized by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group C2/c with a = 27.572(3), b = 5.5064(5), c = 23.310(2) , = 124.785(1)o, C15H19Cdo.5ON2O3, Mr =331.52, V = 2906.6(5) ?, Z = 4, Dc = 1.515 g/cm3, F(000) = 1368 and = 0.801 mm-1. The final R = 0.0403 and wR = 0.1014 for 1795 observed reflections with I≥4(I). The centrosymmetric Cd(II) is six- coordinated in a distorted octahedral geometry, and the dapm in a trans mode acts as a monoden- tate ligand. The intermolecular hydrogen bonds among coordinated aqua molecules with coordi- nated acetate oxygen atoms and uncoordinated dapm nitrogen atoms form a two-dimensional supramolecular framework.

Synthesis and Crystal Structure of {Cu_2(pdc)_2(4,4'-bipy)(H_2O)·3H_2O}_2

The title compound {Cu2(pdc)2(4,4?-bipy)(H2O)3H2O}2 1 (H2pdc = pyridine-2,6- dicarboxylic acid, also known as dipicolinic acid; 4,4?-bipy = 4,4?-bipyridine) has been synthesized by the hydrothermal reaction and its structure was determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group Pi with a = 7.2278(3), b = 10.6259(4), c = 17.7614(6) ? a = 79.5990(10), = 83.6300(10), ? = 71.8280(10)o, V = 1272.60(8) ?, C48H44Cu4N8O24, Mr = 1371.07, Z = 1, Dc = 1.789 g/cm3, = 1.747 mm-1, F(000) = 696, R = 0.0397 and wR = 0.1137 for 3938 observed reflections (I > 2s(I)). There are two kinds of Cu coordination environments, and each central copper(II) atom is five-coordinated in a distorted square-based pyramidal coordination geo- metry. Four copper(II) atoms are linked by four pdc and two 4,4?-bipy ligands to form an annular rectangle structure. Extensive hydrogen-bonding interactions involving carboxylate O atoms as well as coordinated and free water molecules lead to the formation of a three-dimensional network struc- ture.

Synthesis and Crystal Structure of a Salicylaldehyde Ethylene Diamine Schiff Base Manganese (Ⅲ) Complex

The title compound, [Mn(salen)(salicyl)]?.5H2O ( H2salen = N, N?ethylenebis- (salicylideneaminato), Hsalicyl = salicylaldehyde), has been obtained from the reaction system containing (o-HOC6H4CH=NCH2)2, o-HOC6H4CHO and Mn(ClO4)2?H2O in EtOH solvent and structurally characterized. It crystallizes in the monoclinic, space group P21/c with a = 13.0548(4), b = 13.9254(4), c = 11.6630(1) ? b = 105.199(2)? V = 2046.09(9) ?, Z = 4, C23H22MnN2O5.5, Mr = 469.37, Dc = 1.524 g/cm3, F(000) = 972, m = 0.687mm-1 . R = 0.0630 and wR = 0.1142 for 1901 observed reflections with I >2(I). The Mn(Ⅲ) is coordinated by N(1), N(2), O(1) and O(2) of the Schiff base ligand and phenolate O atom of salicylaldehyde with O(3)Mn distance of 2.050(4) , forming a relatively rare five-coordinate square-pyramidal structure.

Synthesis and Crystal Structure of a Mixed-Valence Trinuclear Manganese Complex: Mn_3O(O_2CPh)_6(Py)_3

A new mixed-valence oxo-centered trinuclear manganese complex Mn3O(O2CPh)6 (Py)3 was prepared in pyridine solvent and its crystal structure has been determined. C57H45O13N3Mn3, Mr =1144. 81, trigonal, space group R3,(No.148), unit cell parameters(H cell): a=b=43. 605 (7), c=15. 756(4), V =25946(10),Z=18, Dc=1.32 g/cm￣3 , F(000) = 10566.The final values of R and Rw are 0. 098 and 0. 087 respectively for 3087 observed reflections with Ⅰ>4σ(Ⅰ). The distances of Mn(1)-O(1), Mn(2)-O(1) and Mn(3)-O(1) are 1.855(10),1. 817(8) and 2. 089 (8), respectively, indicating the title compound is a valence-trapped situation.

Synthesis and Crystal Structure of {[Mn(H_2O)_4(3,3'-?azpy)](3, 3'-azpy)_3(PF_6)_2}_n

The complex {[Mn(H2O)4(3, 3?azpy)](3, 3?azpy)3(PF6)2}n (3, 3?azpy = 3, 3? azobispyridine) has been synthesized and characterized. The crystal (C40H40F12MnN16O4P2, Mr = 1153.76) belongs to the triclinic system, space group P with the following crystallographic parameters: a = 10.761(2), b = 11.040(2), c = 23.365(4) ? a = 85.52(1), b = 82.69(1), g = 70.44(1)? V = 2592.5(8) 3, Dc = 1.478 g/cm3, m(MoKa) = 4.16 cm-1, F(000) = 1174, Z = 2, final R = 0.0493 and wR = 0.1158 for the observed reflections (I > 2.00s(I)). The X-ray analysis revealed that manganese(Ⅱ) cation coordination environment is a distorted octahedral geometry, and the Mn2+ cation is coordinated by four oxygen atoms of water in the equatorial plane, while the two nitrogen atoms of 3, 3?azpy occupy the axial positions. The complex forms a one-dimensional chain structure via 3, 3?azpy bridging ligand.

Synthesis, Crystal Structure and Nonlinear Optical Properties of Nickel(Ⅱ) Complex with Schiff-base Ligand

The nickel(Ⅱ) complex with the new ligand of S-benzyl-b-N-[10-ethyl- phenothiazine-3-methylene]dithiocarbazate(HL) crystallizes in the triclinic system, space group P?with a = 7.516(1), b = 11.322(1), c = 13.366(1) , a = 84.818(1), b = 81.688(1), g = 76.037(1), V = 1090.26(3) 3, Z = 1, Dc = 1.413 g/cm3, F(000) = 482, m(MoKa) = 0.774 mm-1 (l = 0.7103 ?, R = 0.0573 and wR = 0.1375 for 3357 observed reflections with I ≥ 2s(I). The HL has lost a proton from its tautomeric thiol form and acts as a single negatively charged bidentate ligand coordinating to the nickel ion via the mercapto sulfur and b-nitrogen atoms. The geometry around Ni(Ⅱ) is almost square-planar with two equivalent NiN and NiS bonds. The nonlinear absorption of HL and NiL2 solutions (in DMF) was measured by open-aperture Z-scan technique at the wavelength of 532 nm.

Solid-state Synthesis at Low-heating Temperature and Crystal Structure of a Dinuclear Molybdenum Complex with Oxalate Ligand[Bu_4N]_2[Mo_2O_2(OH)_2Cl_4(C_2O_4)]

The title compound was synthesized by the solid-state reaction of (NH_4)_6Mo_7O_(24)·4H_2O, Na_2C_2O_4, NH_2OH·HCl and Bu_4NBr at 90 ℃ for 10 h and crystallized from acetone-ether. The green crystal belongs to the monoclinic space group P2_1/n with a=9. 908(2), b= 17, 873(2), c= 13/450(2) A , β= 90. 09(1 )°,V = 2381. 6 (7 ) A￣3 , D_c = 1. 359 g/cm￣3 , Z= 2. The structure was refined to R =0. 0427 for 2562 reflections. The anion of the title compound can be described as an oxalate ligand (C_2O4￣2 ) bridging two [MoCl_2O(OH)] units, which contain Mo(V)atoms.

Synthesis and Structural Characterization of [(C_2H_5)_4N][V^((V))O_2(OC_6H_3(OCH_3)CHNNCSNH_2)]·H_2O

The reaction of tetraethylammonium metavanadate, （Et4N）VO3, with isovanillin semithiocarbazone（VSTC）, HOC6H3（OCH3）CH=NNHCSNH2, in a mixed solvent of ethanol, water and DMSO yields the mononuclear dioxovanadate（V） complex, [（C2H5）4N][V（V）O2 （OC6H3- （OCH3）CHNNCSNH2）](H2O （C17H31N4O5SV, Mr = 454.5） and its single-crystal structure has been determined by X-ray diffraction. The crystal belongs to orthorhombic space group P212121 with unit cell parameters a = 12.940（3）, b= 15.414（3）, c = 10.703（2） ?, V = 2134.8（11） ?3, Z=4, Dcalc = 1.414 Kg/m3, ( = 0.597 mm-1, and F（000） = 960. The final agreement factors are R = 0.076 and Rw=0.096 for 1600 observed independent reflections with F ≥4.0(（F）. The structure revealed that the vanadium atom is bound to two terminal oxygen atoms and one tridentate donor ligand in a distorted square pyramidal arrangement. The sulphur-nitrogen-oxygen donor Schiff-base ligand in the thiol form rather than the thione form is coordinated to the vanadium via the mercapto sulphur, the (-nitrogen and the hydroxylate oxygen.

Synthesis and Structure of the Manganese Complexwith 2-Aminopyridine N-oxide

The complex Mn(apo)6Cl2 (apo=2-aminopyridine N-oxide) was obtained by the reaction of MnCl2(4H2O with apo(HCl and NaOH in ethanol. A single-crystal X-ray study shows that the complex is mononuclear with octahedral coordination environment (MnC30H36N12O6Cl2). The oxygen atoms from apo ligands coordinate to the manganese atom forming Mn(apo)6Cl2. The compound Mn(apo)6Cl2 is hexagonally symmetric with space group R3, lattice constants: a = 12.010(2), b = 12.010(2), c = 20.232(4) ?, ( = 120(, V= 2527.4(7) ?3, Z=3, Mr =786.55, Dc=1.550 g/cm3, (= 0.614mm-1, F(000) = 1221, R = 0.0541, Rw = 0.0580 for 1229 reflections with I>2((I). The distances between Mn(II) and O atoms are in the range from 2.171(5) to 2.184(5) ?, and the distance between the chlorine anion and N atom of amido group is 3.3 ?. The dihedral angle between two adjacent pyridine ring planes is 59.19 (0.17)°.

Synthesis and Crystal Structure of an Ion- pair Compound: [HL]_2[Ni(CN)_4]·4H_2O (L = 4-(2- Hydroxyphenyl)-1,5, 9-triazacyclododecan-2-one)

An ion-pair compound, [HL]2[Ni(CN)4]4H2O 1 has been obtained as an unexpected product when we attempt to prepare a heterometallic cyano-bridged complex by the reaction of GdCl3nH2O, K2Ni(CN)4 and L (L=4-(2-hydroxyphenyl)-1,5,9-triazacyclododecan-2-one) in aqueous solution, and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/n with a = 12.380(1), b = 9.9637(8), c = 17.087(1) ? ?= 105.947(2)? V = 2026.6(3) ?, Rint = 0.0509, Z = 2, Dc = 1.297 g/cm3, C34H56O8N10Ni, Mr = 791.60, F(000) = 844, m(MoKa) = 0.538 mm1, S = 1.030, the final R = 0.0644 and wR = 0.1299 for 2023 observed reflections with I ≥ 2(I). The title compound 1 contains one anion of [Ni(CN)4]2, two cations of [HL]+ and four packing water molecules, which are held together by the NH···O and OH···O hydrogen bonds to form a three- dimensional framework.

Synthesis and Crystal Structure of a Three-dimensional Manganese(Ⅱ)Complex Constructed via Covalent and Hydrogen Bonds

The assembly of 1,4-benzenedicarboxylic acid (H2bdc), 4,4?bipyridine (4,4?bipy), trimethyltin chloride and MnBr24H2O in hydrothermal conditions gave rise to a hydrogen-bonded three-dimensional complex {[Mn(4,4?bipy)4H2O](bdc)}n which has been characterized by single- crystal X-ray diffraction. The complex crystallizes in the monoclinic system, space group P2/n with a = 7.0001(2), b = 11.5540(3), c = 11.4192(1) ? = 101.754(2)? V = 904.21(4) 3, Z = 2, C18H20MnN2O8, Mr = 447.30, Dc = 1.643 g/cm3, F(000) = 462 and m(MoK? = 0.783 mm-1. The final R and wR are 0.0499 and 0.1301, respectively for 1335 observed reflections with I ≥ 2(I). The Mn (Ⅱ) is six-coordinated in a distorted octahedral geometry. 4,4?Bipyridine in a m-bridge mode links [Mn(H2O)4]2+ into a linear cation chain. bdc acts as a counter anion and links the linear chains into a three-dimensional structure through hydrogen bonds.