金属有机框架材料的合成及运用的研究进展

本文主要介绍金属有机框架(MOFs)材料的合成方法及运用,并对有机金属框架材料在今后的研究方向与运用进行了展望。

Synthesis and Re-refinement of Cu_3PSe_4

The title compound Cu3PSe4 was synthesized by the reaction of CuCl, P2Se5 and Se in a molar ratio of 1:1:1 at 500 C and structurally characterized by X-ray crystallography. The crystal belongs to orthorhombic, space group Pmn21 with cell parameters: a = 7.685(2), b = 6.656(1), c = 6.377(1) , V = 326.2(1) 3, Z = 2, Dc = 5.472 g/cm3, Mr = 537.43, F(000) = 476, m = 32.12 mm-1, R = 0.0642, wR = 0.1481 and S = 1.037. The 3-D structure can be regarded as constructed from the alternately stacking of [Cu(2)Se4] tetrahedral layers and Cu(1)PSe tetrahedral layers along the b direction, in which the Cu(2)Se layer is comprised of corner-sharing [Cu(2)Se4] tetrahedra along the a and c directions, and the Cu(1)PSe layer is consisted of alternately corner-sharing [Cu(1)Se4] tetrahedra and [PSe4] tetrahedra along the a and c directions.

π-π Stacking Force in the Solid Structure of Mixed-Metal Complexes: Zn(phen)_2MS_4 (M=W, Mo)

The inter-diffusion of N,N-dimethylformamide solution of Zn(phen)2Cl2 and (NH4)2MS4 (M = W, Mo) in an H-shape tube produced crystals of Zn(phen)2WS4 1 and Zn(phen)2MoS4 2 (phen = 1,10-phenanthroline). The structures of isomorphous complexes 1 and 2 have been determined by X-ray single-crystal structure analyses. Four nitrogen atoms from the phenanthroline ligands and two sulfur atoms from the MS42- anion forming a distorted octahedron coordinate each zinc atom. Through p-p interactions of adjacent aromatic rings of the phenanthroline ligands, a quasi one-dimensional zigzag-stacking column is formed in each complex. Complex 1 crystallizes in monoclinic space group C2/c, with a = 10.447(8), b = 22.016(9), c = 12.824(8) ? b = 103.56(6)? V = 2867.7(8) 3, Z = 4, C24H16N4S4WZn, Mr=737.90, Dc = 1.71 g/cm3, F(000) = 1424, m = 5.25 mm-1, the final R = 0.054 and Rw = 0.075 for 2315 observations with I > 3s (I). Complex 2 crystallizes in monoclinic space group C2/c, with a = 10.410(6), b = 22.095(7), c = 12.830(6) ? b = 103.19(8)? V = 2873.1(5) 3, Z = 4, C24H16MoN4S4Zn, Mr=649.99, Dc = 1.50 g/cm3, F(000) = 1296, m = 1.58 mm-1, the final R = 0.072 and Rw = 0.100 for 1631 observations with I > 3s(I).

The Search for New Methods of Synthesis Possible of Organometallic Compounds of P, As, Sb, Bi

The authors spent the search for new methods of synthesis possible of organometallic compounds of phosphorus, arsenic, antimony, bismuth. For modifications classical reactions the N （nitrogen） atoms have been replaced on atoms of P （phosphorus）, As （arsenic）, Sb （antimony） and Bi （bismuth）. The authors have proposed a new mechanism for the possible reactions.

Synthesis and Crystal Structure of a Cyano-bridged Bimetallic Complex:[NdFe(CN)_6(DMF)_4(H_2O)_3]H_2O

A new bimetallic cyano-bridged complex, [NdFe(CN)6(DMF)4(H2O)3]H2O (DMF = N,N-dimethylformamide) 1, has been obtained by the reaction of hexacyanoferrate potassium with neodymium (Ⅲ) chloride in H2O/EtOH/DMF (volume ratio: 2:2:1), and its structure was determined by means of single-crystal X-ray diffraction. The compound crystallizes in space group P21/n of monoclinic system with cell parameters: a = 17.646(1), b = 8.9011(3), c = 19.945(1) ? b = 95.835(2)? V = 3116.6(3) ?, Z = 4, Dc = 1.536 g/cm3, Mr = 720.66, F(000) = 1456, m = 2.166 mm-1, R = 0.0386, wR = 0.1120 and S = 1.061. The central Nd (Ⅲ) ion is coordinated by seven oxygen atoms of four DMF molecules and three water molecules and one nitrogen atom of the bridging cyanide in a slightly distorted square-antiprism arrangement, and the Fe (Ⅲ) ion is in an almost octahedral environment coordinated to six cyano-ligands, of which one cyanide ligand bridges the Nd (Ⅲ) ion to form a bimetallic complex. Molecules of complexes in the crystal lattice are held together by hydrogen bonding, forming a three-dimensional framework.

Novel Synthesis Method of Nonst0ichiometric Na2-xlrO3 Crystal Structure, Transport and Magnetic Properties

Transition metal oxides with 4d or 5d metals are of great interest due to the competing interactions, of the Coulomb repulsion and the itineracy of the d-electrons, opening a possibility of building new quantum ground states. Particularly the 5d metal oxides containing Iridium have received significant attention within the last years, due to their unexpected physical properties, caused by a strong spin orbit coupling observed in It（IV）. A prominent example is the Mott-insulator Sr2IrO4. Another member of this family, the honeycomb lattice compound Na2IrO3, also being a Mott-insulator having, most probably, a Kitaev spin liquid ground state. By deintercalating sodium from Na2IrO3, the authors were able to synthesize a new honeycomb lattice compound with more than 50% reduced sodium content. The reduction of the sodium content in this layered compound leads to a change of the oxidation state of iridium from ＋ IV to ＋ V/＋ VI and a symmetry change from C2/c to P-3. This goes along with significant changes of the physical properties. Besides the vanishing magnetic ordering at 15 K, also the transport properties changes and instead insulating semiconducting properties are observed.

Designed synthesis of cobalt-oxide-based nanomaterials for superior electrochemical energy storage devices

Cobalt oxides, such as C0304 and CoO, have received increasing attention as potential anode materials for rechargeable lithium-ion batteries （LIBs） owing to their high theoretical capacity. Nanostructure engineering has been demonstrated as an effective approach to improve the electrochemical performance of electrode materials for LIBs. In this review, we summarize recent developments in the rational design and fabrication of various cobalt oxide-based nanomaterials and their lithium storage performance, including 1D nanowires/belts, 2D nanosheets, 3D hollow/hierarchical structures, hybrid nanostructures with carbon （amorphous carbon, carbon nanotubes and graphene） and mixed metal oxides. By focusing on the effects of their structure on their electrochemical performance, effective strategies for the fabrication of cobalt oxide/carbon hybrid nanostructures are highlighted. This review shows that by rational design, such cobalt-oxide-based nanornaterials are very promising as next generation LIB anodes.

Metallafurans and their synthetic chemistry

Based on isolobal analogy,the definition of metallafuran was described and its synthetic chemistry was briefly summarized.In the structure of furan,when one of CH groups was replaced by an isolobal metal fragment ML n(M=metal;L=ligand),the corresponding organometallic complex was called metallafuran,which should be two possible isomers called a-metallafuran(metal fragment at a-carbon of original furan)and b-metallafuran(metal fragment at b-carbon of original furan).As an organometallic complex,a-metallafuran has two resonant forms:one can be viewed as carbonyl coordinated vinyl metal complex and the other can be viewed as alkoxymetal carbene.Therefore,a-metallafuran was also called chelated vinyl ketone metal complex or oxametallacyclopentadiene in the early literatures.For synthesis of metallafurans,a-metallafurans were very common and easily prepared,for example,from alkynes insertion into acyl metal complexes and so on.While there were rare examples reported for b-metallafurans.In this mini review,the synthetic chemistry of metallafuran was mainly focused on its formation mechanism.