蝎型螯合过渡金属配合物的研究(Ⅰ)──氢三(3-对甲氧基苯基吡唑-1)硼酸铜(Ⅱ)配合物的合成、表征及晶体结构

合成了一种蝎合配体氢三(3-对甲氧基苯基吡唑-1)硼酸钾KTp^An.室温下,等物质的量的KTp^An与Cu(O₂CMe)₂·H₂O在THF溶液中反应得配合物[Cu(O₂CMe)(HB{pz^An}₃)](Ⅰ);KTp^An与等物质的量的无水CuCl₂反应则得不同的产物CuCl(pz^AnH)(HB{pz^An}₃)(Ⅱ).对标题化合物进行了元素分析、红外光谱、顺磁共振谱和电化学研究.配合物Ⅰ和Ⅱ的苯溶液的EPR谱研究表明中心金属铜的基态电子构型为拟轴对称的{dx₂-y₂}¹.Ⅱ的X射线衍射晶体结构分析表明,铜离子的配位环境为畸变的四方锥结构,与其配位的有配体Tp^An上3个吡唑氮原子、3-对甲氧基苯基吡唑氮原子和1个氯离子,晶体属空间群P2₁/c.a=1.1643(2)nm,b=2.7081(5)nm,c=1.4494(3)nm,β=105.37(3)°,V=4.4066(14)nm³,Z=4,R=0.0604.分子中存在弱的分子内氢键N-H…Cl,其中Cl₁…N₁=0.3009nm,∠Cl1…H1B-N1=120.3°.     

Taibaihenryiin C的构型、构象及晶体结构

从太白山产的鄂西香茶菜中分离得到新骨架的二萜类化合物TaibaihenryiinC,对其进行X射线衍射晶体结构分析,确定其分子中各取代基的相对构型、环构象及晶体结构.研究表明,C-3位的羟基和C-11位的乙酰氧基以C-20位的甲基为参考均位于β位;分子中的A环为椅式构象,B,C环接近于船式构象,D环接近于信封式构象.特别是在D环中存在较大的扭转角,使D环中有内应力存在,这表明该化合物具有潜在的生理活性.TaibaihenryiinC的晶体结构属正交晶系,P2₁2₁2₁空间群,晶胞参数a=0.6162(1)nm,b=1.2730(1)nm,c=2.5193(3)nm,Z=4.在晶体中分子间通过C-3位的-OH氢与C-11位的乙酰氧基上的羰基氧形成分子间氢键,使分子在晶体中沿a轴呈螺旋结构排列.     

两种具有氢键网络的Ni(Ⅱ)-咪唑配合物的晶体结构和磁性

合成了两种配合物晶体[Ni(im)₆](NO₃)(OH)(H₂O)₄(Ⅰ)和[Ni(im)₄(H₂O)₂][C₆H₄(COO)₂](Ⅱ)(im=C₃H₄N₂).晶体结构测定表明,晶体(Ⅰ)属于六方晶系,空间群P6₃/m,a=0.8985(10)nm,c=2.1002(4)nm,V=1.4685(4)nm₃,Z=2,R=0.043,R_w=0.045.晶体(Ⅱ)属单斜晶系,空间群C2/c,a=2.2207(4)nm,b=0.7665(2)nm,c=1.6043(3)nm,β=120.60(3)°,V=2.3503(9)nm₃,Z=4,R=0.056,R_w=0.079.两种配合物在结构上的突出特点是通过氢键形成了三维无限伸展的氢键电荷传递体系,对分子间电子传递有调节和促进作用,从而对晶体的磁性质产生了一定影响。     

第一个含桥基大环配体的CuⅡ-CoⅡ-CuⅡ异三核配合物的合成和结构

报道了结构新颖的异三核配合物[Co{Cu(μ-L>(N₃)₂}₂(H₂0)₂]·2H₂O的合成和晶体结构(H₂L:2,3-二羰基-1, 4, 8, 11-四氮杂十四烷).三核配合物由含有草酰胺外延桥基的大环铜(Ⅱ)配合物作为"配合物配体"与金属钴离子(Ⅱ)反应得到.晶体属单斜晶系,P2(l)/c空间群.a=0.77172(4) nm, b=1.531 30(3) nm, c=1.47298(7) nm,β=98.540(2)°, V=1.72137(13) nm³,Z=2,R=0.0843.晶体中包含三核配合物单元和溶剂水分子,并通过分子间氢键连成一维链状结构.     

L-(-)-α-苯乙胺类立方烷结构2-萘甲酸二聚体盐的晶体结构

L-(-)-α-苯乙胺与消旋的类立方烷结构2-萘甲酸二聚体相互作用形成铵盐,其晶体结构表明,L-(-)-α-苯乙胺与类立方烷结构2-萘甲酸二聚体作用形成的铵离子通过氢键N_2A-HN_2B…O_5A和N_1A-HN_1A…O_3A与类立方烷结构2-萘甲酸二聚体结合在一起.同时类立方烷结构2-萘甲酸二聚体的两个对映异构体之间也存在分子间氢键O_1A-H_1AA…O_6A和O_1B-H_1AB…O_6B.这些氢键将类立方烷结构2-萘甲酸二聚体的两个对映异构体连在同一个晶胞中,呈现两条分子链状堆积.     

二(四氢糠基茚)稀土氯化物的合成及晶体结构

将四氢糠基茚锂分别与无水三氯化钇和无水三氯化钆以摩尔比2;1反应,除去不溶物和溶剂后,将产物在甲苯/THF中冷冻得到晶体(C₄H₇OCH₂C₉H₆)₂LnCl[Ln=Y(1);Ln=Gd(2)].这两种配合物都是单分子无溶剂化合物,在空气中稳定.配合物1和2的晶体结构都属于正交晶系,P2₁2₁2₁空间群,晶胞参数分别为a=1.04252(9)nm,b=1.47455(12)nm,c=1.49799(13)nm,Z=4,Dc=1.508g/cm³;a=1.03701(10)nm,b=1.47233(12)nm,c=1.51354(14)nm,Z=4,Dc=1.699g/cm³.它们的结构相似,但空间构象不同.稀土中心离子分别与两个茚中的五元环和两个氧原子及氯原子成键,形成九配位结构.     

尿素-富马酸根-水分子为主体晶格的四乙基铵离子包合物的合成与晶体结构

合成一种新的尿素-阴离子复合主体晶格包合物,(C₂H₅)₄N⁺[C₄H₂O₄^2-]1/2·CO(NH₂)₂·H₂O,并进行了X射线晶体结构分析.晶体为单斜晶系,C₂/_c(No.15)空间群,a=1.7909(5)nm,b=1.4431(4)nm,c=1.4443(3)nm,β=126.76(2)°,V=2.9905(13)nm³,Z=4,R₁=0.0647,_wR=0.0735.包合物中,两个尿素分子通过一对N-H…O氢键以通常的“肩并肩”方式连接起来,形成一个二聚体.这些二聚体沿c轴方向依次排列,每两个相邻二聚体间生成的氢键将它们连接成一个沿(001)方向延伸的锯齿形扭带.由c滑移面相关连的富马酸阴离子以水分子为桥,由O(W)-H…O氢键连成一条宽带,沿c轴方向延伸.这些富马酸根-水分子复合氢键宽带与尿素纽带交替平行排列,由此形成了一个平行于ac面的氢键层.四乙基铵离子层填充在b=1/4和b=3/4处的主体晶格的层间空隙处,构成“三明治”式夹层结构的包合物.     

双(2,4-二甲基戊二烯基)氯化钆的合成及晶体结构

合成双(2,4-二甲基戊二烯基)氯化钆{[2,4-(CH₃)₂C₅H₅]₂GD_cl}₂,并测定了晶体结构.晶体为单斜晶系,P2₁/n空间群.晶胞参数a=0.89141(18)nm,b=1.4486(3)nm,c=1.15925(15)nm,β=92.996(18)°,V=1.4949(4)nm³,Z=3.     

硫酸根和碳酸根桥联的双核铁(Ⅲ)配合物晶体结构及紫外-可见光谱研究

室温下合成了硫酸根和碳酸根桥联的双核铁()配合物{2[(TPA)₂Fe₂O(SO₄)](ClO₄)₂·1.5H₂O(1),[(TPA)₂Fe₂O(CO₃)](ClO₄)₂·CH₃OH(2)},并用X射线衍射测定了其晶体结构.结果表明,配合物1为单斜晶系,空间群为P2₁/c,a=1.150(2)nm,b=2.659(5)nm,c=2.933(5)nm,β=99.40(3)°,R=0.0564,wR=0.1106.配合物2为单斜晶系,空间群为P2₁/c,a=1.1368(3)nm,b=1.8280(5)nm,c=2.0542(5)nm,β=94.867(5)°,R=0.0567,wR=0.1362.研究了室温下的紫外-可见光谱性质.     

NH4VO3在NH4H2PO4-H2O和(NH4)3PO4-H2O体系中的溶解度

采用等温溶解法测定了偏钒酸铵(NH₄VO₃)在NH₄H₂PO₄-H₂O和(NH₄)₃PO₄-H₂O体系中T = 298.15-328.15 K时的溶解度以及溶液的密度和pH值。结果表明, NH₄VO₃的溶解度随着(NH₄)₃PO₄或NH₄H₂PO₄溶液浓度的增大,先降低后升高,这是由于同离子效应、化学反应平衡及离子活度的共同作用。比较T = 298.15K时, NH₄VO₃分别在NH₄H₂PO₄-H₂O、(NH₄)₂HPO₄-H₂O和(NH₄)₃PO₄-H₂O体系中溶解度,发现在相同的磷酸盐浓度下, NH₄VO₃的溶解度在NH₄H₂PO₄-H₂O体系中最大,在(NH₄)₃PO₄-H₂O体系中居中,在(NH₄)₂HPO₄-H₂O体系中最小。进一步地,在T = 298.15 K和磷酸盐浓度C = 0.5 mol·kg^-1时,结合pH值和反应溶度积常数K_SP等计算三个体系中的平均离子活度系数(γ_±),发现γ_±值在(NH₄)₂HPO₄-H₂O体系中最大,在(NH₄)₃PO₄-H₂O体系中居中,在NH₄H₂PO₄-H₂O体系中最小,与溶解度规律一致。     

α-甘氨酸晶体的动态磁手性和磁电效应

利用变温直流磁化率测定, 在外加磁场强度为依1 T, 磁场平行于晶体b轴, 发现在301-302 K α-甘氨酸有动态磁手性相变. α-甘氨酸晶体的每个晶胞包含四个分子, 属于具有中心对称结构的P21/n群, 电荷中心对称, 不导电. 在晶体中, 两层之间的N+(3)—H(8)…O(1)和N+(3)—H(8)…O(2)氢键, 沿b轴相互交叉反向配对排列. 在303 K, 用原子力显微镜可观察到α-甘氨酸晶体表面分子层与层间有规则的交叉螺旋排列. 结合中子衍射确定相变机制为, 在相变温度及外加磁场H=±1 T时, α-甘氨酸中的N+(3)—H(8),电子自旋反转为(↑). 因为N+(3)—H(8)…O(1)和N+(3)—H(8)…O(2)两反向氢键的强度和键角不同, 由动态磁手性和磁电效应, 产生电荷中心不对称, 导致304 K附近的热电相变.     

DFT analysis of NMR scalar interactions across the glycosidic bond in DNA

The relationship between the glycosidic torsion angle chi, the three-bond couplings (3)J(C2/4-H1') and (3)J(C6/8-H1'), and the one-bond coupling (1)J(C1'-H1') in deoxyribonucleosides and a number of uracil cyclo-nucleosides has been analyzed using density functional theory. The influence of the sugar pucker and the hydroxymethyl conformation has also been considered. The parameters of the Karplus relationships between the three-bond couplings and chi depend strongly on the aromatic base. (3)J(C2/4-H1') reveals different behavior for deoxyadenosine, deoxyguanosine, and deoxycytidine as compared to deoxythymidine and deoxyuridine. In the case of (3)J(C6/8-H1'), an opposite trans to cis ratio of couplings is obtained for pyrimidine nucleosides in contrast to purine nucleosides. The extremes of the Karplus curves are shifted by ca. 10 degrees with respect to syn and anti-periplanar orientations of the coupled nuclei. The change in the sugar pucker from S to N decreases (3)J(C2/4-H1') and (3)J(C6/8-H1'), while increasing (1)J(C1'-H1') for the syn rotamers, whereas all of the trends are reversed for the anti rotamers. The influence of the sugar pucker on (1)J(C1'-H1') is interpreted in terms of interactions between the n(O4'), sigma*(C1'-H1') orbitals. The (1)J(C1'-H1') are related to chi through a generalized Karplus relationship, which combines cos(chi) and cos(2)(chi) functions with mutually different phase shifts that implicitly accounts for a significant portion of the related sugar pucker effects. Most of theoretical (3)J(C2/4-H1') and (3)J(C6/8-H1') for uracil cyclo-nucleosides compare well with available experimental data. (3)J(C6/8-H1') couplings for all C2-bridged nucleosides are up to 3 Hz smaller than in the genuine nucleosides with the corresponding chi, revealing a nonlocal aspect of the spin-spin interactions across the glycosidic bond. Theoretical (1)J(C1'-H1') are underestimated with respect to the experiment by ca. 10% but reproduce the trends in (1)J(C1'-H1') vs chi.     

双甲基化大豆苷元磺酸盐的合成、晶体结构及活性研究

以大豆苷元为原料合成了强水溶性异黄酮类化合物7,4′-二甲氧基异黄酮-3′-磺酸钠(1)和7,4′-二甲氧基异黄酮-3′-磺酸铜(2).X射线单晶衍射分析表明,化合物1的分子组成为[Na(H₂O)₂](C₁₇H₁₃O₄SO₃),Na的配位数为6,且相邻钠离子以7,4′-二甲氧基异黄酮-3′-磺酸根氧原子桥连,与两个磺酸根的3个氧原子和1个S原子组成六元环,六元环通过Na-O配位键彼此稠合,在晶体结构中形成延伸的锯齿状聚合八面体配位钠离子链;这些钠离子链之间又通过配位水与配位水、磺酸根之间的氢键作用自组装成二维结构的超分子离子聚合物.化合物2的分子组成为[Cu(H₂O)₆](C₁₇H₁₃O₄SO₃)₂·8H₂O,Cu(Ⅱ)位于对称中心上.[Cu(H₂O)₆]²⁺,C₁₇H₁₃O₄SO^-₃和H₂O之间存在多种氢键;并且异黄酮环反平行排列存在π…π的堆积作用.氢键和π…π的堆积作用使化合物2自组装成三维结构的超分子.抗缺氧缺血活性试验结果表明,它们的抗缺氧缺血活性比大豆苷元的高.     

Hydrothermal Synthesis and Structure of[{Mo_8V_4O_(36)(VO_4)(VO)_2}n]~(7n-)Bi-capped α-Keggin Fragments Linked to a Chain

The title compound, (H2en)3H3O{Mo8V4O36(VO4) (VO)2} ?4H2O, was hydrothermally synthesized and structurally characterized by means of IR, ESR spectrum and single crystal X-ray diffraction. It crystallized in a monoclinic system with space group P21/c, a=1. 980 4(4) nm, 6=2. 063 4(4) nm, c=l. 192 0(2) nm, =94. 76(3)?and deep black colour. The compound contains V-centered bi-capped a-Keggin fragments {Mo8V7O42} that are linked together by edge-shared units V O5 via V桹梀 bonds, forming a chain.     

{Mo102}型纳米多孔无机富勒烯衍生物的合成、表征及三阶非线性光学性质

在室温酸性条件下, 利用高负电性的表面分布有20个{Mo9O9}型纳米孔道的无机富勒烯囊状阴离子[{(MoⅥ)Mo5ⅥO21(H2O)6}12{Mo2ⅤO4(SO4)}30]72-与胍基乙酸反应, 得到了表面分布有20个{Mo6O6}型纳米孔道的由102个Mo及氧原子组成的[{(Mo)Mo5O21(H2O)4SO4}12{MoⅤO(H2O)}30]12-小无机富勒烯囊状阴离子. 通过单晶X射线衍射、元素分析、FTIR、UV-Vis、TG-DTA、ESR等手段对其进行了表征. 该化合物属于三斜晶系, P1空间群, 晶胞参数a=2.5377(5) nm, b=2.5932(5) nm, c=3.9547(8) nm, α =83.58(3) °, β=86.15(3) °, γ=75.55(3) °, V=25.023(9) nm3. 利用脉冲时间为5 ns的532 nm激光通过Z-扫描实验得到该化合物的三阶非线性折射率γ=-3.29×10-18 m2/W, 三阶非线性极化率χ(3)=-1.04×10-23 m2·V-2, 表明该化合物具有较强的自散焦三阶非线性光学效应.     

配位聚合物{[Co2(HBTC)2(H2O)6]·C4H10N2·2H2O}n的水热合成、结构表征及荧光性质

采用水热法合成了配位聚合物[Co2(HBTC)2(H2O)6]·C4H10N2·2H2O}n(H3BTC为1,3,5-均苯三羧酸,C4H10N2为哌嗪),通过X射线单晶衍射、红外光谱和荧光光谱进行表征,并用TGA研究了该配位聚合物的热稳定性.晶体属三斜晶系,P1空间群,a=1.05437(9)nm,b=1.05485(9)nm,c=0.71482(5)nm,α=102.4623(28)°,β=91.3500(42)°,γ=111.0186(29)°,V=0.72018(10)nm3,Mr=764.37,Dc=1.762g·cm-3,Z=1,μ(MoKα)=1.25mm-1,F(000)=394,R=0.0307,wR=0.0815.晶体的基本构建单元中包含2个Co()中心、2个配位的HBTC分子和6个配位的水分子.基本构建单元通过相互链接形成具有“Z”型结构的一维配位聚合链,链间通过两种不同的氢键(O—H…O和N—H…O)相互作用,进而形成具有三维骨架结构的微孔晶体,微孔大小为0.71nm×0.82nm.荧光光谱表明,常温下用λex=312nm的光激发后,配位聚合物在329nm处出现强烈的荧光发射.     

Synthesis, characterizations and luminescent properties of terbium complexes with methoxy derivatives of 2'-hydroxy-2-phenylacetophenone

The complexes Tb(L(1))(3).2H(2)O (I) {where L(1)=2'-hydroxy-4'-methoxy-2-phenylacetophenone}, Tb(L(2))(3).2H(2)O (II) {where L(2)=2'-hydroxy-4'-methoxy-2-(p-methoxyphenyl)acetophenone}, Tb(L(3))(3).2H(2)O (III) {where L(3)=2'-hydroxy-4',6'-dimethoxy-2-phenylacetophenone} and Tb(L(4))(3).2H(2)O (III) {where L(4)=2'-hydroxy-4',6'-dimethoxy-2-(p-methoxyphenyl)acetophenone} were synthesized and characterized by IR spectroscopy, TGA/DTA and elemental analysis. The qualitative analysis of the complexes to detect the presence of terbium has been performed by energy dispersive analysis (EDAX). The synthesized complexes on exposure to UV light (354 nm) emit green luminescent with main peak at 546 nm. The complexes emitting bright green colour might be promisingly applicable for optical devices and solid-state lamps for general illumination purposes.     

[C6N2H18]2[Mo5O15(HPO4)2]·H2O的水热合成与结构表征

通过水热法合成了一个新化合物[C6N2H18]2[Mo5O15(HPO4)2]·H2O,并通过IR光谱、ICP、元素分析、差热与热重分析和X射线单晶衍射分析等手段进行了表征.结果表明,晶体属三方晶系,P3(2)21空间群,a=1.1231(1)nm,c=2.2802(5)nm,V=2.4911(7)nm3,Dx=2.835Mg/m3,Z=6,最后的一致性因子R=0.0227,wR=0.0675.阴离子中Mo5O15构成一环状结构,2个HPO4一个连在环的下方,一个连在环的上方,形成类似于“飞碟”状的结构,阳离子为2个质子化的四甲基乙二胺.     

Layered manganese 4-phosphonoisophthalates （4-piH4） embedding Mn-O chains with metamagnetism in Mn3（4-piH）2（H2O）3·H2O

Two manganese phosphonates Mn3(4-piH)2(H2O)3·H2O (1) and Mn5(4-piH)2(4-piH2)2(phen)2(H2O)4 (2) (4-piH4 = 4-phosphonoisophthalic acid, phen = 1,10-phenanthroline) have been synthesized under hydrothermal conditions in the presence of organic co-ligand. Both compounds exhibit layer structures but with different topologies. In compound 1, a complicated "ladder-like" chain of {Mn3O3}O2 which contains three- and six-member rings made up of triangular shaped {Mn3O3} trimers is found. The chains are linked by the PO3C groups to form an inorganic layer. The phenyl and protonated carboxylate groups are pendent between the layers with extensive hydrogen bonds. In compound 2, tetramers of {Mn4O6} are connected by the {MnO6} octahedra through corner-sharing to form an infinite chain, which is further bridged by 4-piH3- ligands into a thick hybrid layer. Magnetic measurements reveal that antiferromagnetic interactions are dominant in both compounds. Metamag- netism is observed in compound 1 at low temperature, while no long range ordering is found in compound 2 down to 1.8 K.     

Hydrothermal Synthesis and Crystal Structure of a New Sandwich—type Molybdenum Phosphate

1 INTRODUCTION The synthesis of porous and open-framework transition metal phosphates has received great in- terest due to their various compositions and topolo- gyies, as well as their useful properties such as con- trollable size- and shape-selectivity, rigid frame- works and chemical/thermal stability[1]. Of these phosphates constructed from oxometal polyhedra and PO4 tetrahedron, the most interesting is the [MoV6P4X31]n－ (X=O, OH) family with the dimen- sionalities ranging from …