Low temperature Mössbauer spectra and magnetic ordering of lithiated ferric molybdate: Li2Fe2(MoO4)3

Powder x-ray diffraction, variable temperature magnetic susceptibility, and zero field Mössbauer spectroscopy measurements were used to characterize the new phase Li₂Fe₂ (MoO₄)₃. This material is obtained topochemically simply by the mixing of solutions of lithium iodide in acetonitrile with solid Fe₂(MoO₄)₃ at ambient temperature. Li₂Fe₂(MoO₄)₃ possesses the high temperature orthorhombic ferric molybdate $$\begin{gathered} Fe_2 (MoO_4 )_3 + 2LiI\xrightarrow{{CH_3 CN}}Li_2 Fe_2 (MoO_4 )_3 + I_2 \hfill \\ (solid)(solution)(solid)(solution) \hfill \\ \end{gathered}$$ structure. Guinier photographs were completely indexed in space group Pnca. Magnetic hyperfine splitting of the zero field Mössbauer spectrum below 12.5 K indicates a three-dimensional magnetically ordered state which susceptibility results show to be weakly ferromagnetic owing to probable canting of antiferromagnetically coupled sublattices.     

On the low temperature magnetic properties of some sulfites of divalent iron

Zero field Mössbauer spectra and powder susceptibility measurements show that the condensed, hydrogen bonded network compound FeSO₃ 3H₂O orders antiferromagnetically (T_Néel 9.5 K). The related anhydrous material FeSO₃ also shows antiferromagnetic exchange but no evidence of long range three-dimenstional magnetic order to as low as 1.4 K.Supported by the U.S. National Science Foundation Division of Materials Research—Solid State Chemistry Program Grant No. DMR 8313710.     

Pore Structure Analysis of Porous Particles by Equivalent Model

Starting from Wheeler's composite theory, which takes both the multilayer adsorption and the capillary condensation into consideration, and assuming the equivalent cylindrical model, we have deduced a strict and relatively simpler formula for the calculation of pore size distribution by solving the integral equation directly. The formula is more convenient for application because of its recursion form. Following the same line of reasoning and using the mean value theorem of definite integrals under different conditions, we have unified the equations of Barrett-Joyner-Halenda, Dubinin, Cranston-Inkley, Dollimore-Heal and Roberts. A table of parameters which is required in the calculation is given. Besides the adsorption of nitrogen, the adsorption with water vapor as the adsorbate is investigated and the corresponding empirical equation of adsorption thickness is given.     

Synthesis, band structure, and optical properties of Ba2ZnV2O8

A novel compound Ba₂ZnV₂O₈ has been synthesized in high temperature solution reaction and its crystal structure has been characterized by means of single crystal X-ray diffraction analysis. It crystallizes in monoclinic system and belongs to space group P2₁/c with a=7.9050(16), b=16.149(3), , β=90.49(3). It builds up from 1-D branchy chains of [ZnV₂O₈⁴⁻]_∞, and the Ba²⁺ cations are located in the space among these chains. The IR spectrum, ultraviolet-visible diffuse reflection integral spectrum and fluorescent spectra of this compound have been investigated. The calculated results of energy band structure by the density functional theory method show that the solid-state compound of Ba₂ZnV₂O₈ is an insulator with direct band gap of 3.48 eV. The calculated total and partial density of states indicate that the top valence bands are contributions from the mixings of O-2p, V-3d, and Zn-3d states and low conduction bands mostly originate from unoccupied antibonding states between the V-3d and O-2p states. The V-O bonds are mostly covalence characters and Zn-O bonds are mostly ionic interactions, and the ionic interaction strength is stronger between the Ba-O than between the Zn-O. The refractive index of n_x, n_y, and n_z is estimated to be 1.7453, 1.7469, and 1.7126, respectively, at wavelength of 1060 nm for Ba₂ZnV₂O₈ crystal.     

Further explorations on bridged 1,2,4-trioxanes

Three new bicyclo[3.2.1]-type 1,2,4-trioxanes have been designed and synthesized. One of them demonstrates better tolerance of the intramolecular hemiketals to steric crowding in hydroperoxidation. The other represents a prototype for possible manipulation of the transient radicals generated in cleavage reactions. A new substitution pattern in the bridged system is explored through synthesis of the third molecule. The configurations of all stereogenic centers in the bridged system can be effectively controlled by the chirality of the allyl alcohol as illustrated by the enantioselective synthesis of the fourth molecule. Finally, similar bicyclo[3.3.1]-type 1,2,4-trioxanes are shown very difficult to be synthesized because of the involvement of a conformer with two substituents at axial positions at the same time.     

Organic phase conversion of bulk (wurtzite) ZnO to nanophase (wurtzite and zinc blende) ZnO

We describe the all-organic phase conversion of bulk commercial ZnO in the wurtzite modification to sub-30 nm ZnO that we find to be partially in the zinc blende [, a=4.568(3) Å] modification. The conversion involves refluxing ZnO in 2,4-pentanedione (acetylacetone) at 413 K to form the zinc 2,4-pentanedionate, which is decomposed by heating at 573 K in an appropriate high-temperature solvent such as dibenzylether to form nanophase ZnO. This nanophase, partially zinc blende ZnO can also be obtained in a single step by heating commercial zinc 2,4-pentanedionate in refluxing dibenzylether. Thermodiffractometry suggests that the conversion of zinc blende ZnO to wurtzite ZnO commences near 650 K.     

Unusually sharp dependence of water exchange rate versus lanthanide ionic radii for a series of tetraamide complexes

The tetraamide ligand, DOTA-tetra(glycine ethyl ester), forms complexes with the lanthanide(III) cations that exist in solution predominantly as the square antiprism structure with single, slowly exchanging inner-sphere water molecule. Variable-temperature 1H and 17O NMR studies revealed that the bound water lifetimes in these complexes were sharply dependent upon the ionic radius of Ln3+ cation. A novel lanthanide-induced shift technique was used to unmask the bound water 17O resonance of SmL3+ and YL3+ complexes from the bulk water resonance. The bound water lifetime (tauM298) was approximately 800 mus in the EuL3+ complex but became much shorter (several microseconds) for Ln3+ cations with larger and smaller ionic radii. This demonstrates that water exchange is exquisitely fine-tuned in this macrocyclic tetraamide system and that a variety of Ln3+ complexes meet with the exchange requirement, Deltaomega*tauM >/= 1, necessary for an efficient MT agent.     

A Novel pH-Sensitive MRI Contrast Agent

A tetrasubstituted derivative of 1,4,7,10-tetraazacyclododecane with amide coordinating groups and extended noncoordinating phosphonate groups forms a complex with gadolinium(III) (shown in the picture) which contains one slowly exchanging inner-sphere water molecule (tau(M)=21 μs). The 20-MHz water proton relaxivity of the complex was found to be highly pH dependent. Protonation of the noncoordinating phosphonate groups appears to catalyze prototropic exchange of the bound water protons, thereby providing a mechanism for enhanced water contrast below pH 7.     

Sterically demanding diporphyrin ligands and rhodium(II) porphyrin bimetalloradical complexes

A series of sterically demanding diporphyrins H2(por)-X-(por)H2 ligands that contain spacers (X) with different degrees of flexibility were synthesized from the trimesitylporphyrin derivatives 5-(4-hydroxyphenyl)-10,15,20-trimesitylporphyrin (TMP-OH)H2 (1a) and 5-(2,6-dimethyl-4-hydroxyphenyl)-10,15,20-trimesityl-porphyrin, (DMTMP-OH)H2 (1b). The monomeric porphyrins 1a,b, which have steric demands similar to that of tetramesitylporphyrin, (TMP)H2, and carry a hydroxyl functional group at the para position of one of the mesophenyl substituents, were constructed from reaction of pyrrole with two aromatic aldehydes by a mixed aldehyde condensation approach. The diporphyrins with alkyl diether tethers were obtained stepwise from reactions of the hydroxy functionalized porphyrins 1a,b with dibromides Br(CH2)nBr. The diporphyrin which contains a more rigid m-xylylene spacer, was made directly from reaction of 1b with alpha,alpha'-dibromo-m-xylene. Rhodium was inserted into the porphyrins using Rh2(CO)2Cl2 and converted to dimethyl complexes Me-Rh(Por)-X-(Por)Rh-Me. The dirhodium(II) derivatives .Rh(por)-X-(por)Rh.) were generated by photolysis of the dimethyl complexes and observed to occur as stable bimetalloradicals because the ligand steric demands prohibit Rh(II)-Rh(II) bonding. EPR spectra of the dirhodium(II) derivatives, triphenyl phospine adducts, and dioxygen complexes are reported. The kinetic advantage of bimetalloradical complexes for substrate reactions that have two metal-centered radicals in the transition state is demonstrated by reactions of dihydrogen with dirhodium(II) bimetalloradical complexes.     

Development of a modified beta-cyclodextrin based fluorosensor for dipyridamole

2,6-O-diethyl-β-cyclodextrins were prepared and immobilized onto silica gel to develop a fluorosensor for dipyridamole. The analytical performance characteristics of the proposed sensor for analysis of dipyridamole were as follows: the detection limit was 0.8 nmol/L with a relative standard deviation of 1.4% for 10 determinations of 50 nmol/L of dipyridamole. The modification of β-CD improved the sensitivity and selectivity for measuring dipyridamole. The recommended method has been successfully tested for the determination of dipyridamole in clinical samples (urine and pharmaceutical preparations). Received: 23 January 1997 / Revised: 14 April 1997 / Accepted: 21 April 1997