High-temperature molecular magnets based on cyanovanadate building blocks: spontaneous magnetization at 230 k

The molecular-based magnetic materials Cs(2)Mn(||)[V(||)(CN)(6)] (1) and (Et(4)N)(0.5)Mn(l.25)- [V(CN)(5)].2H(2)O (2) (where Et is ethyl) were prepared by the addition of manganese(II) triflate to aqueous solutions of the hexacyanovanadate(II) ion at 0 degrees C. Whereas 1 crystallizes in a face-centered cubic lattice, 2 crystallizes in a noncubic space group. The cesium salt (1) has features characteristic of a three-dimensional ferrimagnet with a Néel transition at 125 kelvin. The tetraethylammonium salt (2) also behaves as a three-dimensional ferrimagnet with a Néel temperature of 230 kelvin; only two other molecular magnets have higher magnetic ordering temperatures. Saturation magnetization measurements indicate that in both compounds the V(II) and high-spin Mn(II) centers are antiferromagnetically coupled. Both 1 and 2 exhibit hysteresis loops characteristic of soft magnets below their magnetic phase-transition temperatures. The high magnetic ordering temperatures of these cyano-bridged solids confirm that the incorporation of early transition elements into the lattice promotes stronger magnetic coupling by enhancing the backbonding into the cyanide pi* orbitals.     

Oxygen-carrying iridium complexes: kinetics, mechanism, and thermodynamics

The rates of oxygenation and deoxygenation of a series of iridium complexes increase and decrease, respectively, with increasing electron-releasing tendency of the anionic ligands (A) attached to the metal atom in the oxygencarrying compounds, [IrA(CO)(Ph(3)P)(2)]. Calculated heats of oxygenation (-DeltaH(2)(0)), related to Ir-O(2) bond energies, are proportional to the previously reported O-O bond lengths in the oxygen adducts, [O(2)IrA(CO)(Ph(3)P)(2)].     

Pentaborate Polyanion in the Crystal Structure of Ulexite, NaCaB5O6(OH)6{middle dot}5H2O

Triclinic ulexite crystals contain isolated borate polyanions [B(5)O(6)(OH)(6)](3-) related to the well known pentaborate polyanion [B(5)O(6)(OH)(4)](-) by addition of two hydroxyl groups to two opposite B-O triangles. The isolated ulexite polyanions form the [B(5)O(7)(OH)(4)](n)(3n-) chains previously found in crystals of the related mineral probertite, NaCaB(5)O(7)(OH)(4).3H(2)O.     

An Inorganic Double Helix: Hydrothermal Synthesis, Structure, and Magnetism of Chiral [(CH3)2NH2]K4[V10O10(H2O)2(OH)4(PO4)7]{middle dot}4H2O

Very complicated inorganic solids can be self-assembled from structurally simple precursors as illustrated by the hydrothermal synthesis of the vanadium phosphate, [(CH(3))(2)NH(2)]K(4)[V(10)O(10)(H(2)O)(2)(OH)(4)(PO(4))(7)].4H(2)O, 1, which contains chiral double helices formed from interpenetrating spirals of vanadium oxo pentamers bonded together by P(5+). These double helices are in turn intertwined with each other in a manner that generates unusual tunnels and cavities that are filled with (CH(3))(2)NH(2)(+) and K(+) cations, respectively. The unit cell contents of dark blue phosphate 1, which crystallizes in the enantiomorphic space group P4(3) with lattice constants a = 12.130 and c = 30.555 angstroms, are chiral; only one enantiomorph is present in a given crystal. Magnetization measurements show that 1 is paramagnetic with ten unpaired electrons per formula unit at higher temperatures and that antiferromagnetic interactions develop at lower temperatures.     

Electrochemical growth of highly conducting inorganic complexes

The formation of single crystals of highly conducting inorganic complexes, for example, K(2)Pt(CN)(4)X(0.3) . 3H(2)O (X = Cl, Br), K(1.75)Pt(CN)(4) . 1.5 H(2)O, or K(1.64)Pt(O(2)C(2)O(2)) . 2H(2)O, has been effected via electrochemical growth from concentrated aqueous solutions of potassium tetracyanoplatinate(II) and potassium bis(oxalato)platinate(II).     

Synthesis, structure, and reactivity of an iron(V) nitride

Despite being implicated as important intermediates, iron(V) compounds have proven very challenging to isolate and characterize. Here, we report the preparation of the iron(V) nitrido complex, [PhB((t)BuIm)(3)Fe(V)≡N]BAr(F24) (PhB((t)BuIm)(3)(-) = phenyltris(3-tert-butylimidazol-2-ylidene)borato, BAr(F24) = B(3,5-(CF(3))(2)C(6)H(3))(4)(-)), by one electron oxidation of the iron(IV) nitrido precursor. Single-crystal x-ray diffraction of the iron(V) complex reveals a four-coordinate metal ion with a terminal nitrido ligand. M??bauer and electron paramagnetic resonance spectroscopic characterization, supported by electronic structure calculations, provide evidence for a d(3) iron(V) metal center in a low spin (S = 1/2) electron configuration. Low-temperature reaction of the iron(V) nitrido complex with water under reducing conditions leads to high yields of ammonia with concomitant formation of an iron(II) species.     

Crystal Structure of Kernite, Na2B4O6(OH)2 {middle dot} 3H2

Kernite, Na(2)B(4)O(6)(OH)(2). .3H(2)0, contains parallel infinite chains of the borate polyanion[B(4)O(6)(OH)(2)](n)(2n-). The chains are composed of six-membered rings containing one boron-oxygen triangle and two boron-oxygen tetrahedra. The rings are linked through commonly shared boron-oxygen tetrahedra.     

Fresnoite: unusal titanium coordination

The crystal structure of fresnoite, Ba(2)(TiO)[Si(2)O(7)], consists of [Si(2)O(7)](6-) double groups and titanium-centered square pyramids linked to form flat sheets. Intercalated between these sheets are Ba(2+) ions in highly distorted pentagonal antiprisms. The structure of fresnoite is related to that of melilite, (Ca,Na)(2)(Mg,Al[Si(2)(7)].     

Size-Specific Infrared Spectra of Benzene-(H2O)n Clusters (n = 1 through 7): Evidence for Noncyclic (H2O)n Structures

Resonant ion-dip infrared spectroscopy has been used to record size-specific infrared spectra of C(6)H(6)-(H(2)O)n clusters with n = 1 through 7 in the O-H stretch region. The O-H stretch spectra show a dramatic dependence on cluster size. For the n = 3 to 5 clusters, the transitions can be divided into three types-attributable to free, pi hydrogen-bonded, and single donor water-water O-H stretches-consistent with a C(6)H(6)-(H(2)O)n structure in which benzene is on the surface of a cyclic (H(2)O)n cluster. In n = 6 and 7 clusters, the spectra show distinct new transitions in the 3500 to 3600 wave number region. After comparison of these results with the predictions of ab initio calculations on (H(2)O)n clusters, these new transitions have been assigned to double donor O-H stretches associated with the formation of a more compact, noncyclic structure beginning with (H(2)O)(6). This is the same size cluster for which ab initio calculations predict that a changeover to noncyclic (H(2)O)n structures will occur.     

Aluminum-rich apatite

More than 25 atomic percent of aluminum can susbtitute for other cations in the structure of apatite [A(10)(XO(4)) (6)Z(2)]. Such a synthetic product was obtained by expelling volatile constituents (H(2)O and F) from morinite during thermal treatment. Infrared absorption spectra, chemical analysis, and x-ray powder diffraction demonstrate that the aluminum has two coordination numbers, and more than twice as much aluminum substitutes for calcium (A position) as for phosphorus (X position).     

Metal oxide chemistry in solution: the early transition metal polyoxoanions

Many of the early transition elements form large polynuclear metal-oxygen anions containing up to 200 atoms or more. Although these polyoxoanions have been investigated for more than a century, detailed studies of structure and reactivity were not possible until the development of modern x-ray crystallographic and nuclear magnetic resonance spectroscopic techniques. Systematic studies of small polyoxoanions in inert, aprotic solvents have clarified many of the principles governing their structure and reactivity, and also have made possible the preparation of entirely new types of covalent derivatives such as CH(2)Mo(4)O(15)H(3-), C(5)H(5)TiMo(5)O(18)(3-), and (OC)(3)Mn(Nb(2)W(4)O(19))(3-). Since most early transition metal polyoxoanions have structures based on close-packed oxygen arrays containing interstitial metal centers, their chemistry offers a rare opportunity to study chemical transformations in detail on well-defined metal oxide surfaces.     

Oxygen binding in cyanmet hybrid and normal hemoglobins: applicability of sequential and two-state concerted models

The cyanmet hybrid hemoglobins alpha(2)beta(+CN)(2) and alpha(+CN)(2)beta(2) are widely held to be similar or equivalent in structure and subunit interactions to the partially oxygen-liganded species alpha(2)(beta * O(2))(2) and (alpha * O(2))(2)beta(2), respectively. An analysis of precise data on oxygen binding to the cyanmet hybrids and normal hemoglobin shows that if this is the case, then cooperative ligand binding in hemoglobin is more properly described by some model of the sequential type than by any twostate concerted model.     

微量重金属对水螅摄食行为的毒性研究

[目的]为水螅毒理学研究提供技术支持。[方法]分别探索3种微量重金属离子(Cu2+、Cr6+、Zn2+)抑制水螅摄食和摄食反应的最低可见效应浓度(LOEC)。[结果]Cu2+、Zn2+、Cr6+抑制水螅摄食的LOEC分别为0.014、0.51和6×10-5mg/L,其抑制水螅摄食反应的LOEC分别为0.030、.55和8×10-5mg/L。Cu2+、Zn2+、Cr6+对水螅摄食反应的无可见效应浓度(NOCE)分别是0.01、0.5和6×10-5mg/L。Cu2+、Zn2+、Cr6+对水螅的摄食行为均具有明显的抑制作用,其毒性为Cr6+>Cu2+>Zn2+。[结论]利用水螅的不同摄食特性来检测水体的微毒毒性是可行的。该技术具有较高的检测效率,优于常规的动物浸泡方法。     

Kinetic evidence for five-coordination in AlOH(aq)2+ ion

Trivalent aluminum ions are important in natural bodies of water, but the structure of their coordination shell is a complex unsolved problem. In strong acid (pH < 3.0), Al(III) exists almost entirely as the octahedral Al(H2O)6(3+) ion, whereas in basic conditions (pH > 7), a tetrahedral Al(OH)(4- structure prevails. In the biochemically and geochemically critical pH range of 4.3 to 7.0, the ion structures are less clear. Other hydrolytic species, such as AlOH(aq)2+, exist and are traditionally assumed to be hexacoordinate. We show, however, that the kinetics of proton and water exchange on aqueous Al(III), coupled with Car-Parrinello simulations, support a five-coordinate Al(H2O)4OH2+ ion as the predominant form of AlOH(aq)2+ under ambient conditions. This result contrasts Al(III) with other trivalent metal aqua ions, for which there is no evidence for stable pentacoordinate hydrolysis products.     

大豆蛋白-三聚氰胺-尿素-甲醛树脂胶黏剂固化剂的研究

以大豆蛋白降解液、三聚氰胺、尿素和高浓度甲醛为原料,合成了一种低摩尔比的大豆蛋白-三聚氰胺-尿素-甲醛共缩聚树脂胶黏剂(SMUF)。选用(NH4)2SO4、(NH4)2S2O8、(NH4)2HPO4和H3PO4作为SMUF树脂的固化剂,研究了固化剂对SMUF树脂基本理化性能的影响。结果表明:1)传统固化剂(NH4)2SO4不能使SMUF树脂充分固化,最终树脂胶合强度低、耐水性差,固化后的胶层断面疏松、多孔;2)H3PO4和(NH4)2S2O8属于中强酸体系,两者均能一定程度加速SMUF树脂的固化,树脂胶合强度和耐水性均得到改善,固化温度显著降低,固化放热量有所提高;3)(NH4)2HPO4是一种缓冲型酸,其催化SMUF树脂的固化速度较为均匀,树脂综合性能较优,树脂的胶合强度和耐水性较好,固化温度也有所降低,树脂交联程度高,树脂固化层断面相对较为均匀。     

Hg~(2+)与Cr(VI)对富营养化水体中藻类生长的毒性效应

[目的]研究Hg2+与Cr(VI)对富营养化水体中藻类生长的毒性效应,为富营养化水体的生物监测以及生物修复提供参考依据。[方法]分别用不同浓度的Hg2+、Cr(VI)以及两者的混合营养液培养从富营养化水体中分离的藻母液,观察Hg2+与Cr(VI)对藻类生长繁殖的毒性效应。[结果]富营养化水体中的藻类对Cr(VI)表现相当敏感,当Cr(VI)浓度超过1mg/L时即对藻类的生长产生了明显的影响。在Hg2+浓度较低时,藻类对Hg2+不是十分敏感,当Hg2+浓度增大至一定程度,毒性愈来愈强,而Cr(VI)毒性效应则相反。当离子浓度小于10mg/L时,Hg2+对藻类的毒性低于Cr(VI),大于10mg/L时,Hg2+毒性超过Cr(VI)。Hg2++Cr(VI)混合离子对藻类生长的抑制具有协同作用,但只有当浓度超过4mg/L时才表现出来。[结论]重金属离子对藻类的毒性不但与藻细胞本身有关,还与重金属离子的浓度有关。     

A late-transition metal oxo complex: K7Na9[O=PtIV(H2O)L2], L = [PW9O34]9-

Terminal mono-oxo complexes of the late transition metal elements have long been considered too unstable to synthesize because of repulsion between the oxygen electrons and the mostly filled metal d orbitals. A platinum(IV)-oxo compound flanked by two polytungstate ligands, K7Na9[O=Pt(H2O)L2], L = [PW9O34(9-)], has now been prepared and isolated at room temperature as air-stable brown crystals. X-ray and neutron diffraction at 30 kelvin revealed a very short [1.720(18) angstrom] Pt-O bond and no evidence of a hydrogen atom at the terminal oxygen, ruling out a better precedented Pt-OH complex. Density functional theory and spectroscopic data account for the stability of the Pt(IV)-oxo unit by electron withdrawal into delocalized orbitals of the polytungstates.     

Boron-Oxygen Polyanion in the Crystal Structure of Tunellite

The crystal structure of tunellite, SrO.3B(2)O(3).4H(2)O, with infinite sheets of composition n[B(6)O(9)(OH)(2)](2-), has cations and water molecules in the spaces within the sheets. Adjacent sheets are held together by hydrogen bonding through the water molecules. The boron-oxygen polyanions provide the first example in hydrated borate crystals of one oxygen linked to three borons.     

Structure of a three-dimensional, microporous molybdenum phosphate with large cavities

The synthesis, single-crystal x-ray structural characterization, and sorption properties of a microporous molybdenum phosphate, (Me(4)N)(1.3)(H(3)O)(0.7)[Mo(4)O(8)(PO(4))(2)] . 2H(2)O (Me, methyl), are presented. The three-dimensional framework is built up from Mo(4)O(8)(4+) cubes and PO(4)(3-) tetrahedra that are connected in such a way that large, cation-filled voids are generated; these voids constitute 25% of the volume of the solid. Absorption isotherms for water show the completely reversible uptake of 4 to 5 percent by weight water into the micropores of this compound, which corresponds to 10 to 12 percent by volume.     

Synthesis of inorganic fullerene-like molecules

The reaction of [Cp*Fe(eta5-P5)] with Cu(I)Cl in solvent mixtures of CH2Cl2/CH3CN leads to the formation of entirely inorganic fullerene-like molecules of the formula [[Cp*Fe(eta5:eta1:eta1:eta1:eta1:eta1-P5)]12[CuCl]10[Cu2Cl3]5[Cu(CH3CN)2]5] (1) possessing 90 inorganic core atoms. This compound represents a structural motif similar to that of C60: cyclo-P5 rings of [Cp*Fe(eta5-P5)] molecules are surrounded by six-membered P4Cu2 rings that result from the coordination of each of the phosphorus lone pairs to CuCl metal centers, which are further coordinated by P atoms of other cyclo-P5 rings. Thus, five- and six-membered rings alternate in a manner comparable to that observed in the fullerene molecules. The so-formed half shells are joined by [Cu2Cl3]- as well as by [Cu(CH3CN)2]+ units. The spherical body has an inside diameter of 1.25 nanometers and an outside diameter of 2.13 nanometers, which is about three times as large as that of C60.