4-(2-吡啶偶氮)间苯二酚盐酸盐的晶体结构

用SYNTEXP3/R3四圆衍射仪收集4-(2-吡啶偶氮)间苯二酚盐酸盐晶体的三维衍射数据。晶体属P2₁/c空间群,a=11.339Å,b=6.835Å,c=18.170Å,β=102.76°,Z=4。利用Patterson法及直接法测定了晶体结构。经位置坐标参数,各向异性温度因子及比例因子块矩阵最小二乘修正后,最后的R值为0.055。晶体结构分析结果表明:4-(2-吡啶偶氮)间苯二酚的分子内所有非氢原子共面并形成大的共轭体系。氯离子及二个结晶水与分子中的N,O形成氢键,起到桥联分子的作用。     

8-羟基喹啉(HQ)钇、镍离子加合物[YQ(HQ)2][NiQ3](ClO4)的合成及晶体结构

合成了标题化合物并测定其晶体结构,该晶体为单斜晶系,P21/c空间群,晶胞参数:a=16.972(4)Å,b=14.128(3)Å,c=22.615(4)Å,β=103.16(2)°,V=5280.14Å,F(000)=2264,Z=4。钇和镍均为六配位多面体取畸变八面体构型。讨论了[YQ(HQ)₂][NiQ₈](ClO₄)的红外光谱。     

AGGREGATION OF 2,3-DIHYDROXY-ETIOCHLORIN I. AN AMPHIPHILIC MODEL COMPOUND FOR PHOTODYNAMIC THERAPY AND GREEN HEME d

The crystal structure of 2,3-dihydroxy-etiochlorin I has been determined to obtain information on its aggregation behavior. Cis -dihydroxychlorins serve as model compounds for green heme d and show promising photonecrotic activity in photodynamic therapy. The compound shows strong aggregation in the solid state facilitated by intramolecular hydrogen bonding between one hydroxy group and pyrrole nitrogens of neighboring molecules. This novel type of aggregation leads to chain-type aggregates in the crystal. The title compound 4 crystallized in the monoclinic space group Ia (Z = 4) with unit cell dimensions a = 9.902(4) Å, b = 26.430(9) Å, c = 10.823(5), β= 104.47(3) Å, V = 2743(2) ų. The structure was refined to an R -value of 0.097 on the basis of 1150 reflections with F > 4.0σ (F) (130 K).     

一氯甲酸甲酯二-三苯基膦合铂络合物晶体结构、分子结构的研究

本文确立一氯甲酸甲酯二-三苯基膦合铂络合物是浅黄透明晶体,属于单斜晶系,P2₁/n空间群.并测定了晶胞参数.分子式为Pt[P(C₆H₅)₃)]₂·COOCH₃Cl,该化合物是配位键结合的新型络合物.     

PHOTOLYSIS OF AQUEOUS SOLUTIONS OF POTASSIUM CIS-DIAQUOBIS (OXALATO) CHROMATE (III)

Abstract— The photolysis of aqueous solutions of cis -[Cr(C₂O₄)₂(H₂O)₂]- at 254 nm and pH 4 produced CO₂ and H₂ in nearly equal yields. The quantum yield of hydrogen, φ², increased by 9% and the yield of carbon dioxide, φ, by 65% as the pH was lowered from 4 to I. The total gas yield, φ_gas, decreased in the presence of added oxalate or chromium (II) ions and when the light intensity was lowered. The gas yield in D₂O was appreciably higher than in H₂O. The variation of φ_gas with pH (D) and with added oxalate ion was roughly parallel in the two liquid media. The gas yield increased in the series:
A tentative mechanism is suggested to explain the results.     

1:2型硝酸铀酰二苯并-18-冠-6氢键夹心式配合物的晶体结构

化合物[UO₂(NO₃)₂(H₂O)₂]·(DB18C6)₂晶体属单斜晶系,空间群为P21/k。晶体学参数:a=11.782(2)Å,b=8.584(2)Å,c=22.631(2),β=98.29(2)Å°,Z=2.用3024个I≥3σ(I)的三维X射线独立衍射数据进行结构解析,最终的R=0.066。结构分析表明,两个双齿配体硝酸根及两个水分子配位于线型铀酰离子的赤道平面上,铀的配位数是8,配位几何构型为稍有扭曲的六方双锥。配位水分子的4个氢原子分别与上下两层冠醚环上的氧原子生成氢键。形成夹心式分子缔合物。     

钆、铽、铒、铥的乙酰丙酮三水络合物的晶体结构和分子结构

报导了用X射线衍射法测定的钆、铽、铒、铥的四种乙酰丙酮三水络合物的晶体结构。确定了它们的晶体学参数与原子在晶胞中的分数坐标。讨论了晶体结构与分子结构的特征。     

THE SYNTHESIS AND CRYSTAL STRUCTURE OF CIS-BIS(1,10-PHENANTHROLINE)GLYCINECOBALT(Ⅲ)

A new coordination compound of cis-bis(1,10-phenanthroline)glycinecobalt(Ⅲ)chloridate tetrahydrate,cis-[Co(phen)_2gly]Cl_2.4H_2O,has been prepared by glycinereacted with cis-[Co(phen)_2Cl_2]Cl,then isolated by SP-Sephadex C-25 H~+ form column.The crystal and molecular structure of the new compound has been determined by RIGAKUAFC5R four circle diffractometer,5032 independent reflections were collected ofwhich 3781 observable reflections were used for structure refinement.The crystal ismonoclinic,space group C2/c,with a=35.13(1),b=9.637(3),c=17.485(6),β=115.08(Z)~,V=5362(3),Z=8.The structure was refined by full matrix least-squaresprocedure to a final R=0.041 and R_=0.060.The molecular formula was CoC_(28)H_(28)N_5O_8Cl_2.with molecular weight M_r=636.38,D_c=1.58g/cm~3,μ=8.88cm~(-1)and F_((000))=2624.     

苯并-15-冠-5的配位性能研究

苯并-15-冠-5苦味酸钠配合物单晶由丙酮-乙醇(1:1)溶液中得到,晶体属单斜空间群C_2h⁵-P₂₁/n,晶体学数据:a=11.134(3)Å,6=13.541(3)Å,c=14.927(4)Å,β=93.41(2)°Å,V=2246.4ų,Z=4,晶体结构由直接法解出,晶体结构分析结果表明,与苯环共轭的芳醚氧原子上的电子密度可通过苯环而转移。     

ACTINOMETRY IN MONOCHROMATIC FLASH PHOTOLYSIS: THE EXTINCTION COEFFICIENT OF TRIPLET BENZOPHENONE AND QUANTUM YIELD OF TRIPLET ZINC TETRAPHENYL PORPHYRIN

Abstract— The extinction coefficient ε_T, of triplet benzophenone in benzene has been directly determined by absolute measurements of absorbed energy and triplet absorbance, Δ D ⁰_T, under demonstrably linear conditions where incident excitation energy, E ₀, and ground state absorbance, A ₀, are both extrapolated to zero. The result, 7220 ± 320 M ^-1 cm^-1 at 530 nm, validates and slightly corrects many measurements relative to benzophenone of triplet extinction coefficients made by the energy transfer technique, and of triplet yields obtained by the comparative method.
As E ₀ and A ₀ both decrease, Δ D ⁰_T becomes proportional to their product. In this situation, the ratio R = (1/ A ₀)(dΔ D ⁰_T/d E ₀) = (ε_T - ε_G)φ_T. Measurements of R , referred to benzophenone, give (ε_T - ε_G)φ_T for any substance, without necessity for absolute energy calibration.
Both absolute and relative laser flash measurements on zinc tetraphenyl porphyrin (ε_T - ε_G at 470 nm = 7.3 × 10⁴ M ^-1 cm^-1) give φ_T= 0.83 ± 0.04.     

双(甲基环戊二烯基)二(2,6-二氯苯氧基)铪的晶体和分子结构

本文用X-射线衍射法测定了(η⁵CH₉C₅H₄)₅H₁(OC₆H₉Cl₃-2,6)₂的晶体和分子结构.晶体结构属单科晶系,空间群为P²1/c,晶胞参数为a=17.010(2)Å,b=8.577(1)Å,C=16.313(3)Å,β=101.52(3)°,晶胞内分子数Z=4.分子内有非结晶学二次旋转轴对称性,铪原子周围的两个甲基环戊二烯基和两个氧原子构成一个变形四面体.两个环戊二烯基的平面夹角为125.33°.氧-铪-氧键角为103.71°.铪-氧键长为2.004-2.022Å,较铪-氧单键键长为短,表明具有部分双键特性.     

原子簇化合物[Et4N]2[Mo2O2S2(S2)(S4)]的合成和结构

目前,Mo-S化合物的化学,特别是以多硫基为配体的铟硫化合物的化学是一个活跃的研究领域。这里我们报道含S₂^2-、S₄^2-两种多硫基的二核钼原子簇化合物〔Et₄N〕₂〔Mo₂O₂(S₂)(S₄)(u₃-S)₂]的合成和单晶结构。     

PRIMARY PRODUCTS OF LIQUID WATER PHOTOLYSIS AT 1236, 1470 AND 1849 Å

Abstract— The yield of the primary products of the liquid water photolysis at 1236 and 1470 Å is reported. It was found that besides the dissociation of the excited water molecules into H and OH radicals probably e⁻_aq is also formed. The H and OH radicals were scavenged by means of formate, and the e⁻_aq together with a part of H₂O* by adding carbon dioxide. The quantum yields determined at 1236 Å, are: Φ(H, OH) = 1.03 & 0.02, 0.06 <Φ( e⁻_aq , H₂O*) < 0.12 and at 1470 Å,: Φ(H, OH)=0.72±0.02, 0.037 < Φ( e⁻_aq , H₂O*) <0.075. The quantum yield of high purity water at 1849 Å in the absence of any scavengers is Φ(H, OH)=0.022. Previously published data by us for 1849 Å are also given: Φ(H, OH)=0.33 ± 0.01 and 0.02 < Φ ( e⁻_aq H₂O*) < 0.04. Reaction mechanisms are proposed.     

The Synthesis, Crystal and Molecular Structure of Tetrakis Dithiocarbamato Molybdenum(Ⅴ)Hexacloromolybdate

The title compound {Mo[S2CN( C2H5)2]4 1{MoCl6}-1 was synthesized,and its crystal structure was determined by X-ray diffraction.It is nionoclinic,space group P21/a with a=14.761(6)A b=16.012(6)A,c=17.108(9)A,β=102.63(4) and Z=4.The coordinates of a molybdenum atom were deduced from the Patterson function,and parameters of other atoms were found from successive Fourier syntheses.The block-diagonal least-siuares refinement for all alons gave final residual factors R=0.0908,Rw=0.0761.     

Phase Diagram of RbI-SmI_2 Binary System and Structural Investigation of RbSm_2I_5 and RbSmI_3

The RbI-SmI2 , binary system was studied with DTA and X-ray powder diffraction. Its phase diagram shows that it has a congruently melting compound,RbSm2I5 , with a melting point 524℃; an incongru-ently melting compound, Rb2SmI4 , with an inconsruently point 467℃ and two compounds, RbSmI3, and Rb3SmI5, being decomposed at 433℃ and 460℃, respectively. The measured structure of RbSm2I5 shows that it is isomorphous with NH4 Pb2 Cl5 space group P21/c, a=10 . 063(3)A, b=9.003(3)A. c =14 . 242(5)A°,β=90.23(3)°;z = 4, MVx= 1 94 . 3cm3/mol;D=5.255g/cm3 and Do =5. 334g/cm3 (25. 0℃).The structural, investigation ofRbSmI3 shows that it belongs to the orthorhombic system with a = 15.914(6)A, b=8.898(3)A c =12.193(5)A; Z=8, MVx =130.0cm3/mol, Dx =4 . 743g/cm3,Do = 4.597g/cm3(25.0℃).     

CHEMILUMINESCENCE AND FLUORESCENCE OF THE EUROPIUM IONS-ADENINE NUCLEOTIDES SYSTEM AND ITS POSSIBLE BIOLOGICAL SIGNIFICANCE

Abstract— Chemiluminescence of the Eu(II)/Eu(III)-adenine nucleotide-H₂O₂ system and fluorescence of the Eu(III)-adenosine triphosphate system have been investigated. The spectral distribution of the chemiluminescence emission has shown an occurrence of three main bands (Λ=470–480,590–620 and ca. 700 nm). The energy transfer process from the adenosine triphosphate molecules to the Eu(III) ions has been observed in the fluorescence spectrum. The examined chemiluminescence and fluorescence spectra show that these both kinds of emission originate from the ⁵ D _***τ⁷F_*** ( n =1–4) transitions in the Eu(III) ions.     

COMPUTER SIMULATION OF EXCITON JUMPING STATISTICS AND ENERGY FLOW IN C-PHYCOCYANIN OF ALGAE Agmenellum quadruplicatum IN THE PRESENCE OF TRAPS

Abstract—Energy migration has been studied in C-phycocyanin (C-PC) rods with traps located in the terminal trimer disc, using the Monte Carlo method and the system of differential equations. It has been found that jump time statistics can be described by the function F = C(t/0>)exp(-t/ < t_o>), where C is the constant, t and < t₀ > are, respectively, the exciton jump time and its averaged value for chromophores of the corresponding spectral types (α 84 , β84 or β155). The values < t₀ > were calculated for the cases of C-PC monomers, trimers and higher associates.
The C-PC model, which consists of three hexamers with traps located in the β84 chromophores of the peripheral trimer, was examined. It was found that the total efficiency of excitation capturing, ø_tr, exceeds 90%, provided "local" quantum yield of energy trapping ø₀ > 10%. The ø₀ value influences both the excitation lifetime (τ) and the mean number of excitation jumps (N_iump) before its conversion. For the ø₀ = 100% and 10%, the corresponding lifetimes and numbers of jumps were calculated to be τ= 75 and 155 ps and N_jump= 105 and 222 jumps, respectively.
The dynamics of excitation redistribution along the C-PC rods and the fluorescence kinetics for various ø₀ values were calculated for C-PC chromophores excited by a +, and the correlation between these processes and ø ₀ , was disclosed. The transient processes of excitation redistribution were shown to proceed within a time period t < 30 ps.     

Syntheses and Structures of (Ga1-xBx)PO4, with a New Modification of High Cristobalite,and (B1-xZnx)PO4, with Low Cristobalite Type

The transition metal element substitutions of the industrial catalytic material ortho-borophosphate, BPO₄, can lead to either new type of structure for Cr^[1] or stabilize low cristobalite structure for Mn, Fe,Co, Ni and Cu^[2] Here we report our results on the substitution by main group elements Zn and Ga. The two title compounds were synthesized by high temperature solid state reactions and the structure were refined by powder diffraction methods.The structure parameters:(B_0.25Ga_0.75)PO₄:Tetragonal, P-4, a=4.727(1), c=7.078(1) Å,V=158.17(1) ų, Z=2, R(P)=0.0965, R(I)=0.0426; (B_0.61Zn_0.39)PO₄:Orthorhombic, C222₁ a=7.080(1), b=7.087(1),c=6.990(1) Å, V=350.71(2) ų, Z=4,R(P)=0.0904,R(I)=0.0438. Pure GaPO₄ were found three kinds of structures, low- and high-cristobalite and high -quartz with an observation of an unknown unstable high cristobalite at high temperature^[3] The boron substitution of the high-cristobalite GaPO₄ with space group I-A leads to lower symmetry space group(P-4). We assume the low symmetry structure related to the unknown unstable phase. The structures of both compounds are similar to very well known cristobalite (see figure below).     

Synthesis,crystal structure,magnetic properties and second harmonic generation of a new noncentrosymmetric coordination compound:Triaqua(4-amino-6-methoxypyrimidine) cuprate(Ⅱ)sulfate

The chemical preparation, crystal structure and infrared spectroscopic characterization of the triaqua(4-amino-6-methoxypyrimidine) cuprate(II) sulfate, [Cu(C_5H_7N_3)(H_2O)_3]SO_4, is reported. The compound crystallizes in the noncentrosymmetric orthorhombic space group P2_12_12_1 with lattice parameters a = 7.9025(3), b = 11.1189(4), c = 12.9720(4) , V = 1139.81(7) ~3 and Z = 4. The Cu(II) cation is fivecoordinated, in an early half-way between square pyramidal and trigonal bipyramidal fashion, by two nitrogen atoms of the 4-amino-6-methoxypyrimidine ligand and three water oxygen atoms. In the atomic arrangement, the organic ligands and the 5-connected Cu centers are linked with each other to give a 1-D corrugated hybrid chain running along the b-axis direction. The chains are interconnected by the SO_4~(2-) anions via O–H...O, O–H...S, C–H...O and N–H...O hydrogen bonds to form layers spreading parallel to the(011) plane. The vibrational absorption bands were identified by infrared spectroscopy. Quantitative measurements of the second harmonic generation(SHG) of a powdered sample at 1064 nm were performed and a relative efficiency of 5.2 times the KDP standard was observed. Magnetic properties were also defined to characterize the complex. Magnetic measurements revealed that this material had a onedimensional antiferromagnetic character. The magnetic parameters were g = 2.11 and 2J/k B = -36 K.     

双呋喃氟脲嘧啶的晶体结构

1,3-双(2′-四氢呋喃)-5-氟脲嘧啶(简称FD-1)晶体属三斜晶系,α=8.911(4),b=11.744(5),c=12.320(7)Å,α=99.69(4)°,β=93.49(4)°,γ=97.83(4)°。空间群为P1,Z=4。R=0.089。对比了FD-1,FT-207和5-Fu三个同系列抗癌药物结构及其抗癌疗效。