两个单核配合物晶态荧光材料的合成、晶体结构及性质

在水中采用蒸发溶剂的方法,合成了两个晶态单核配合物[Co(phen)3]·2H2SPA·0.5HSPA·10H2O(1)和[Ni(phen)2(H2O)2]·H2SPA·0.5HSPA·3H2O(2)(H2SPA'=间苯二甲酸-5-磺酸根阴离子,phen=1,10-邻菲罗啉).在配合物1中,中心离子与三个1,10-邻菲罗啉配位,形成[Co(phen)3]2+.未配位的水分子与阴离子H2SPA-和HSPA2-通过氢键相互连接形成三维的网状结构.在配合物2中,中心离子与两个1,10-邻菲罗啉分子和两个水分子配位,构成阳离子[Ni (phen)2(H2O)2]2+.阳离子[Ni (phen)2(H2O)2]2+与自由的阴离子H2SPA-、阴离子HSPA-和未配位的水分子通过氢键连接形成三维网状结构.室温下两个配合物均具有荧光发射峰,其发射峰分别在460 nm和439 nm.与配体相比,均发生明显的红移.荧光寿命分别为1.1244 ns和1.4882 ns.     

两个晶态异质同构配合物荧光材料的合成、结构及性质

在水中采用蒸发溶剂的方法,合成了两个异质同构的单核配合物[M(phen)2(H2O)2]·2SIPH2·2H2O (M=Zn,Co),SIPH2=间苯二甲酸-5-磺酸根阴离子,phen=1,10-邻菲罗啉).在两个配合物结构单元中,中心离子与两个1,10-邻菲罗啉和两个水分子配位,形成[M(phen)2(H2O)2]2+阳离子.两个未配位的水分子与[M(phen)2(H2O)2]2+阳离子,SIPH2-阴离子通过氢键相互连接形成三维的网状结构.SIPH2-阴离子起到平衡电荷的作用.室温下两个配合物均具有荧光发射峰,其发射峰分别在460 nm和439 nm.与配体相比,均发生明显的红移.荧光寿命分别为1.7638 ms和1.6356 ms.     

二聚体配合物[Mn(1,6-nds)(phen)_2(H_2O)]_2·(CH_3OH)_3·(H_2O)_2的合成、晶体结构及荧光性质

采用水热法合成了二聚体Mn(Ⅱ)配合物[Mn(1,6-nds)(phen)2(H2O)]2·(CH3OH)3·(H2O)2,(1,6-nds=1,6-萘二磺酸根离子,phen=1,10-邻菲罗啉)。采用X射线单晶衍射、红外光谱、热重分析和紫外可见光谱等方法对配合物进行了表征。X射线单晶衍射表征结果表明,该配合物晶体属于三斜晶系,空间群为P-1。锰离子与两个1,10-邻菲罗啉分子、一个水分子和1,6-萘二磺酸根离子配位,形成[Mn(1,6-nds)(phen)2(H2O)]结构单元。这种结构单元、未配位的甲醇和水分子通过两种类型的氢键O-H…O和O-H…S相连,形成三维网状结构。与配体相比,配合物的荧光光谱发生红移,其最大发射峰在439 nm。     

晶态配合物荧光材料[Ni(3,5-(SO3)2 CatH2)(phen)2(H2O)]·4H2O的合成、结构及性质

利用缓慢蒸发溶剂法合成了单核镍(Ⅱ)配合物[Ni(3,5-(So3)2CatH2)(phen)2(H2O)]·4H2O(CatH2=1,2-二羟基苯,phen=1,10-邻菲罗啉).利用X-射线单晶衍射、元素分析、红外光谱、热重分析和荧光光谱等对其进行了表征.结果表明,该配合物属于三斜晶系,P1空间群.镍离子与一个1,2-二羟基苯-3,5-二磺酸根离子、两个1, 1O-邻菲罗啉配体和一个水分子配位,形成[Ni(3,5-(SO3)2CatH2)(phen)2(H2 O)]结构.在结构单元中,还有四个未配位的水分子.未配位的水分子和[Ni(3,5-(SO3)2CatH2)(phen)2(H2 O)]结构通过O-H…O氢键相连,形成三维网状结构.与配体相比,配合物的荧光发射谱发生红移,发射峰在645 nm.荧光寿命为1.07 ns.     

双核钆混配配合物[Gd(Ts-p-aba)3(phen)]2·2DMF·4.4H2O的合成与晶体结构

采用溶剂热合成法合成了双核钆混配配合物[Gd(Ts-p-aba)3(phen)]2·2DMF·4.4H2O(Ts-p-aba-=N-对甲苯磺酰对氨基苯甲酸根离子,phen=1,10-邻菲罗啉,DMF=N,N-二甲基甲酰胺),并利用红外光谱(FT-IR)、热重分析(TG-DSC)和X-射线单晶衍射等实验手段研究了配合物的组成、结构和性质.X-射线单晶衍射结果表明:该配合物晶体属三斜晶系,P1空间群,晶胞参数是:a=1.10505(12) nm,b=1.74570(18) nm,c=1.78163(19) nm,α=70.321(2)°,β=85.357(2)°,γ=82.600(2)°,V=3.2066(6) nm3,Mr=2633.99,Dc=1.364 g/cm3,Z=1,μ=1.197mm-.6个氧原子和2个氮原子在钆离子周围形成一个变形的反四方棱柱体配位环境.配合物存在着丰富的氢键,将配合物连接成二维层状超分子结构.     

2,2联吡啶-5,5-二羧酸与稀土配合物的合成、结构及发光性能

利用2,2-联吡啶-5,5-二羧酸作为配体,采用水热法,合成了稀土配合物[Ln2(bpydc)3·2DMF]n(1,Ln=Eu,Tb;Hbpydc=2,2-联吡啶-5,5-二羧酸).单晶X射线测试表明Tb配合物与Eu配合物具有相同结构.配合物1·Tb属于三斜晶系,P-1空间群,晶胞参数为a=1.39657(2) nm,b=1.40874(1)nm,c=1.45241 (1) nm,α=90.887(1)°,β=115.261(1)°,γ=113.951(1)°,V=2.29931(5) nm3,Z=2;同时,配合物1·Tb具有新颖的三维结构,七个氧原子在稀土离子周围形成一个略微变形的单帽三棱柱配位环境.利用红外光谱、荧光光谱、磷光光谱对配合物进行了表征,结果表明:Eu(Ⅲ)与Tb(Ⅲ)配合物分别在612 nm与542 nm处有强烈的特征荧光发射;配体三重态能级(26178 cm-1)与Eu (Ⅲ)、Tb(Ⅲ)的最低激发态能级匹配,配合物具有优良的能量传递效率.     

两个含氮配体配合物固体荧光材料的合成、晶体结构及性质

采用缓慢蒸发溶剂法在水中合成了两个含氮配体配合物[Co(phen)3] ·3,5-(SO3)2H2Cat·6H2O(1)和[M(py)3(H2O)3]·(1,5-nds) (2)(H2Cat=1,2-二羟基苯阴离子,M=Co0.88Cuo.12,1,5-nds=1,5-萘二磺酸根离子,phen=1,10-邻菲罗啉,py=吡啶).配合物1中,钴离子与三个1,10-邻菲罗啉配位形成[Co(phen)3]2+.六个自由的水分子与3,5-(SO3)2H2Cat阴离子通过氢键相互连接形成二维的层状结构.配合物2中,中心离子是由钴离子和铜离子构成,其与三个吡啶和三个水分子配位,构成[M(py)3(H2O)3]2+.自由的1,5-nds阴离子通过氢键连接[M(py)3(H2O)3]2+,形成三维网状结构.室温下两个配合物均具有荧光发射蜂,其最大发射峰分别在551 nm和340 nm.它们的荧光发射的主要原因分别是配体间电荷转移和配体-金属间电荷转移.     

[Zn(phen)(H_2O)_3SO_4]·H_2O配位聚合物的合成及其晶体结构表征

在乙醇水溶液中合成了标题配位聚合物[Zn(phen)(H_2O)_3SO_4]·H_2O(phen=o-phenanthroline),并进行了元素分析、X射线衍射等表征.X射线衍射结果表明,此配合物属三斜晶系,空间群为P_1~-,晶胞参数为:a=0.8042(3) nm,b=0.8636(8) nm,c=1.1595(1) nm,α=92.067(0)°,β=92.126(0)°,γ=103.761(0)°,V=0.7809(0) nm~3,Z=2,D_c=1.016 g/cm~3,μ=0.876 mm~(-1),F_((000))=424.配合物中的金属锌离子与一个邻菲咯啉、3个水分子和一个硫酸根离子配位,形成一个变形的八面体结构,通过氢键构建为三维超分子配合物.     

{[La(phen-dione)2(H2dhtp)0.5(H2O)]·H2O}n配合物的合成、晶体结构及荧光性质

采用低温水热法合成了一个新的镧(Ⅲ)配位聚合物{[La(phen-dione)2(H2dhtp)0.5(H2O)]·H2O}n(phen-dione＝1,10-邻菲啰啉-5,6-二酮,H2dhtp＝2,5-二羟基对苯二甲酸酯).单晶衍射分析结果表明,该配合物属三斜晶系,P-1空间群,晶胞参数为a＝9.4600(19)nm,b ＝11.810(2)nm,c ＝12.280(3)nm,α＝93.34(3)°,β＝106.74(3)°,γ＝103.21(3)°,V＝1267.7(5)nm3,Dc ＝1.806 g/cm3,Z＝2,μ＝1.752mm-1,F(000)＝678.用X-射线单晶衍射、元素分析、IR、TG和荧光光谱对配合物进行了表征.测量晶体的荧光光谱特性发现,该配合物在488 nm 和532nm有较强的荧光发射峰.     

一种氨基萘磺酸铈配合物的合成、晶体结构和性质

在乙醇/水混合溶剂中合成了一种单核铈配合物[Ce(H2O)2 (phen)2(Ans)3] (phen)·4H2O(1)(其中HAns=4-氨基-1-萘磺酸,phen=邻菲啰啉),并对其进行元素分析、红外光谱、紫外光谱、荧光光谱、热重分析和X-射线单晶衍射等测定.标题配合物属单斜晶系P21/n空间群,a=1.32882(5),b=2.44909(9),c=1.87421 (6) nm,β=9.1214(3) nm,z=4,V=6.0981 (4) nm3,Dc=1.585 g.cm3,μ=0.929 mm-,R1 =0.0612,wR2 =0.1518,S=1.07.配合物中9配位的Ce(Ⅲ)处于畸变的三帽三棱柱配位多面体环境CeN4O5.配位单元[Ce(H2O)2 (phen)2 (Ans)3]与未配位的phen和晶格水通过芳环堆积相互作用和氢键组装形成三维超分子体系.     

Synthesis and crystal structure of a terephthalato-bridged copper(II) complex [Cu2(tpt)(bpy)2(H2O)4] [Cu2(tpt)3 (bpy)2(H2O)2]

A terephthalato-bridged copper(II) complex [Cu₂(tpt)(bpy)₂(H₂O)₄][Cu₂(tpt)₃(bpy)₂ (H₂O)₂] (1) (tpt = terephthalate, bpy =; 2,2'-bipyridine) was synthesized by the reaction of Cu(ClO₄)₂ 6H₂O and terephthalic acid in the presence of 2,2'-bipyridine in H₂O solution. Crystal structure of 1 was determined by X-ray diffraction analysis in the triclinic space group P , with a = 10.7327(10) Å, b = 11.1658(11) Å, c = 17.3768(16) Å, = 108.063(2), = 91.064(2), = 116.721(2), V = 1737.5(3) ų, and Z = 2. Both the anion and the countercation in 1 are copper(II) complexes linked by terephthalate bridges in the bis(monodentate) (syn–anti) mode. The anion and the countercation are also linked by two hydrogen bonds between coordinating water molecules and terephthalate ligand.     

Synthesis and crystal structure of di(2-aminopyrimidinium) trichlorodimethyl(2-aminopyrimidine)stannate(IV) chloride (H-2APY)2[SnMe2Cl3(2APY)]Cl

The synthesis and molecular structure of di(2-aminopyrimidinium) trichlorodimethyl(2-aminopyrimidine)stannate(IV) chloride (H-2APY)₂[SnMe₂Cl₃(2APY)]Cl is reported. The compound crystallized in the orthorhombic space group Pnma with a = 20.524(1) Å, b = 10.822(1) Å, c = 10.472(1) Å and V = 2325.9(3) ų, Z = 4. The structure consists of three fragments: the hexacoordinated organotin anionic complex [SnMe₂Cl₃(2APY)]⁻, which exhibits distorted octahedral geometry; two protonated 2-aminopyrimidinium cations (H-2APY)⁺, and one chloride anion.

     

A Unique Example of a Co-crystal of [Co(AMTTO)2(H2O)2](NO3)2 and [Co(AMTTO)2(CH3CN)2](NO3)2 (AMTTO = 4-amino-5-methyl-1,2,4-triazol-3(2H)-thione)

A co-crystal of cobalt(II) complexes, Co(AMTTO)₂(CH₃CN)₂]²⁺(NO₃)₂. [Co(AMTTO)₂(H₂O)₂]²⁺(NO₃)₂, compound (1) was isolated from the reaction of Co(NO₃)₂?6H₂O and 4-amino-3-mercapto-6-methyl-5-oxo-1,2,4-triazine (AMTTO) in acetonitrile as solvent. Isolated crystals were characterized by elemental analyses, IR spectroscopy as well as X-ray diffraction studies. Crystal data for 1 at 95 K revealed a monoclinic space group P2₁/n, a?=?11.7903(5), b?=?12.1279(5), c?=?14.1443(6) Å, β?=?99.244(4)°, Z?=?2, R₁?=?0.0339. Compound 1 consists of two co-crystallized Co(II) complexes [Co(AMTTO)₂(CH₃CN)₂]²⁺ and [Co(AMTTO)₂(H₂O)₂]²⁺ and four nitrate counter anions In both complexes, cobalt(II) ions are in an octahedral arrangement. Two S, N bidentate AMTTO ligands are coordinated to both Co(II) ions. The coordination sphere of Co1 is completed by two acetonitrile molecules, and these positions are occupied by water molecules for Co2.

Graphic Abstract

A co-crystal of cobalt(II) compound was isolated from the reaction of Co(NO₃)₂?6H₂O and 4-amino-3-mercapto-6-methyl-5-oxo-1,2,4-triazine in acetonitrile as solvent.

     

Crystal structures of mixed compounds Cu(2)Gly(D-Ser)(L-Ser)2 and Cu(2)Gly 3(L-Ser)

-The crystal structures of mixed coordination compounds, Cu(2)Gly(D-Ser)(L-Ser)₂(I) and Cu(2)Gly ₃(L-Ser)(II), which contain the amino acid residues of glycine (Gly) and serine (Ser) in the 1: 3 and 3: 1 ratio, respectively, are studied by electron diffraction. Crystals I and II are triclinic, Z = 1, and space group P1. For I, a = 8.96(2) Å, b = 9.66(2) Å, c = 5.07(2) Å, α = β = 90°, and γ = 92.8(3)°. For II, a = 8.37(2) Å, b = 9.65(2) Å, c = 5.06(2) Å, α = β = 90°, and γ = 92.8(3)°. Compounds I and II have layered structures that are based on the CuGly(L-Ser) fragment. Structures I and II differ mainly in their interlayer spacing and configuration of the interlayer space.     

Molecular structures of (tBu)Ga(S2CNnPr2)2 and (iPrO)Ga(S2CNEt2)2: An example of an unusual ligand pseudorotation

The molecular structures of (^tBu)Ga(S₂CNⁿPr₂)₂ (1) and (ⁱPrO)Ga(S₂CNEt₂)₂ (2) have been determined. The variation in the geometries observed for bis-dithiocarbamate compounds of gallium, (X)Ga(S₂CNMe₂)₂ (X=Cl, ⁱPrO, ^tBu) do not lie along the Berry pseudorotation pathway for the square-based pyramid to trigonal bipyramid geometrical transition. Instead, the structures appear to lie on an unusual ligand two-step, Texas, pseudorotation mechanism which results in a highly distorted trigonal bipyramidal geometry. Crystal data: (1) monoclinic, P2₁,/c, a = 9.786(1), b = 29.218(3), c = 9.452(1) Å, = 108.379(9)°, V = 2564.7(5) ų, and Z = 4. (2) Monoclinic, P2₁ /c, a = 10.980(3), b = 15.673(4), c = 12.461(3) Å, = 97.47(2)°, V = 2126.2(9) ų and Z = 4.     

Crystal structure of [Mn2(III)(salpa)2Cl2(H2O)2] (H2salpa = 1-(salicylaldeneamino)-3-hydroxypropane)

The manganese complex, (Mn₂(III)(salpa)₂Cl₂(H₂O)₂], has been prepared and its structure determined using x-ray crystallography. The dimer is a di-₂-alkoxo complex which is a six-coordinate manganese dimer with unsupported alkoxide bridges and a rare example of a chloride- and water-containing manganese dimer. The complex crystallizes in the monoclinic space group P2₁/c with a = 9.315(5), b = 11.130(4), c = 11.637(5) Å, = 104.33(3)°, V = 1169.0(9) ų, and Z = 2. The structure comprises discrete binuclear clusters in which the metal atoms are bridged by two alkoxo oxygens of the salpa^2– ligands. The Mn—O and Mn—N distances are in good agreement with those found for other manganese(III) Schiff base complexes. The Mn—Cl and Mn—O3 distances are 2.585(2) and 2.371(2) Å, respectively, and the Mn ··· Mn distance is 3.001(1) Å. In the crystal, there are two types of hydrogen bonding between the H₂O molecule and the Cl atom with Cl ··· H(H₂O) distance of 2.33(6) (intramolecule: –1 + x, y, –1 + z) and 2.68(6) Å (intermolecule: –1 + x, 0.5–y, –0.5 + z).     

Crystal and molecular structures of 1-(2-carboxypropan-2-ylamino)-3-(1-naphthyloxy) propan-2-ol (1) (C17H21NO4) and 1-(2-carbamoyl propan-2-ylamino)-3-(1-naphthyloxy) propan-2-ol (2) (C17H22N2O3)

The crystal structures of two new-adrenergic antagonists, derivatives of propranolol containing 2-methylalanine fragment are described in this paper. The space groups and unit-cell parameters are: compound1 (C₁₇H₂₁NO₄): monoclinic, space groupP2₁/n,a=5.787(1),b=18.703(4),c=23.526(5)Å,=96.49(2)°; compound2 (C₁₇H₂₂N₂O₃): triclinic, space groupP¯1,a=8.321(1),b=10.121(1),c=10.368(1)Å,=109.49(1)°,=90.49(1)°, =103.48(1)°. The structures were solved by direct methods and refined with full matrix least-squares techniques toR indices of 0.055 and 0.049, respectively. The molecules of compound1 exist in the crystal as dual ions. The molecules of compound2 are compact and their external chain is twisted in a characteristic way (similar to that found in peptides).     

Crystal structure ofcis-diaqua bis(2,2′-bipyridyl)chromium(III) nitrate, [Cr(bipy)2(H2O)2] (NO3)3

cis-Diaquabis(2,2-bipyridyl)chromium(III) nitrate crystallizes in the mono-clinic system, space groupP2₁/c, witha=16.102(6),b=10.792(5),c=15.076(6) Å,=112.90(5)°, andZ=4. The saltlike structure was determined from X-ray crystallography and refined toR=7.5% for 3342 observed reflections. The Cr atom is octahedrally surrounded by twocis water molecules and by two chelated 2,2-bypiridyl ligands forming two nearly orthogonal planes. Selected bond distances are: Cr-O, 2.00(1) and 1.98(1) Å, Cr-N, 2.04 Å (mean).     

Crystal and molecular structures of 1-(2-methyloxycarbonylo-propan-2-ylamino)-3-(1-naphthyloxy) propan-2-ol hydrochloride (1) (C18H24NO4Cl) and 1-(2-methylcarbamoylpropan-2-ylamino)-3-(1-naphthyloxy) propan-2-ol (2) (C18H24N2O3)

The crystal structures of two new-adrenergic antagonists, derivatives of propranolol, are reported in this paper. The space groups and unit-cell parameters are: compound1 (C₁₈H₂₄NO₄Cl), monoclinic,P2₁,a=7.215(1),b=8.591(1),c=15.017(1)Å,=95.64(1)°; compound2 (C₁₈H₂₄N₂O₃), monoclinic,P2₁/c,a=10.218(3),b=21.616(5),c=8.124(2)Å,=101.28(2)°. The structures were solved with direct methods and refined by full-matrix least-squares techniques toR indices of 0.036 and 0.066, respectively. The molecule of compound1 has an extended external chain, and thus its structure is linear, whereas the molecule of compound2 is compact, and its external chain is twisted in a characteristic way, as is the case of peptides.