Synthesis, Crystal Structure and Characterization of a New Manganese(Ⅱ) Tetracarboxylate

By hydrothermal synthesis, a manganese（H） tetracarboxylate [Mn（2,2′-bipyridi- ne）（btec）0.5（HEO）]En （H4btec = 1,2,4,5-benzenetetracarboxylic acid） was obtained and characterized by single-crystal X-ray diffraction, IR, elemental analysis and thermogravimetric analysis. It crystallizes in triclinic, space group P1, with a = 7.721（4）, b = 8.905（5）, c = 10.712（6）A, a = 80.899（8）, β = 70.371（8）, y = 78.201（8）°, Z = 2, V= 675.8（7）A3, Mr= 354.20, De= 1.741 g/cm^3,μ = 1.007 mm^-1, F（000） = 360, S = 0.956, （△/σ）max = 0.000, the final R = 0.0490 and wR = 0.1262. This compound presents an infinite 1D polymer featuring a double-chain structure. The Mn（Ⅱ） ion is five-coordinated. The four carboxylate groups of btec4- are all deprotonated and coordinated to four Mn atoms in a monodentate fashion, forming a 1D double chain structure with a cavity. Such chains are interconnected by π-π stacking interactions into 2D layers which are further interlinked into a supramolecular structure by hydrogen bonds.

Achieving a superior Na storage performance of Fe-based Prussian blue cathode by coating perylene tetracarboxylic dianhydride amine

Fe-based Prussian blue(Fe-PB)cathode material shows great application potential in sodium(Na)-ion batteries due to its high theoretical capacity,long cycle life,low cost,and simple preparation process.However,the crystalline water and vacancies of Fe-PB lattice,the low electrical conductivity,and the dissolution of metal ions lead to limited capacity and poor cycling stability.In this work,a perylene tetracarboxylic dianhydride amine(PTCDA)coating layer is successfully fabricated on the surface of Fe-PB by a liquid-phase method.The aminated PTCDA(PTCA)coating not only increases the specific surface area and electronic conductivity but also effectively reduces the crystalline water and vacancies,which avoids the erosion of Fe-PB by electrolyte.Consequently,the PTCA layer reduces the charge transfer resistance,enhances the Na-ion diffusion coefficient,and improves the structure stability.The PTCA-coated Fe-PB exhibits superior Na storage performance with a first discharge capacity of 145.2 mAh g^(−1) at 100 mA g^(−1).Long cycling tests exhibit minimal capacity decay of 0.027%per cycle over 1000 cycles at 1 A g^(−1).Therefore,this PTCA coating strategy has shown promising competence in enhancing the electrochemical performance of Fe-PB,which can potentially serve as a universal electrode coating strategy for Na-ion batteries.

Hydrothermal Synthesis and Crystal Structure of a New Zero-dimensional Complex: [Zn(H_2BPTC)(phen)_2]_n·3nH_2O

A new metal-organic coordination complex [Zn（H2BPTC）（phen）2]n.3nH2O （BPTC = 3,3＇,4,4＇-benzophenone tetracarboxylate, phen = 1,10-phenanthroline） 1 has been obtained from hydrothermal reaction and characterized by elementaj analysis, IR, TG and single-crystal X-ray diffraction. In compound 1, the zinc cation is hexa-coordinated with two carboxylate oxygen atoms from one H2BPTC ligand and four nitrogen atoms from two different phen ligands, showing a slightly distorted octahedral geometry. Crystal data： C41H30N4O12Zn, Mr = 836.06, monoclinic, P21/c, a = 14.2714（9）, b = 16.9386（10）, c = 15.0151（9）A, β = 101.3420（10）^o, V= 3558.8（4）A3 Dc = 1.560 g/cm^3,μ（MoKa） = 0.766 mm^-1, F（000） = 1720, Z= 4, R = 0.0439 and wR = 0.1157 for 4123 observed reflections with I 〉 2 o（I）.

Hydrothermal Synthesis and Crystal Structure of a 1D Cu(II) Coordination Polymer: [Cu(bbpy)(H_2bptc)]_n Constructed by a Tetracarboxylic Acid

The title compound [Cu（bbpy）（H2bptc）]n （bbpy = 4,4＇-dimethyl-2,2＇-bipyridine and H4bptc = 1,1＇-biphenyl-2,2？,3,3＇-tetracarboxylic acid） has been synthesized by hydrothermal reaction, and its structure was determined by X-ray diffraction and characterized by elemental analysis, IR spectrum and thermogravimetric analysis. The crystal is of triclinic, space group P1 with a = 11.2831（12）, b = 11.6718（13）, c = 11.7771（13）, α = 105.392（2）, β = 108.382（2）, γ = 112.397（2）o, CuC28H20N2O8, Mr = 576.00, V = 1222.4（2）3, Dc = 1.565 g/cm3, F（000） = 590, μ = 0.951 mm-1, S = 1.022 and Z = 2. The final refinement gave R = 0.0405 and wR = 0.1142 for 4270 observed reflections with I 2σ（I）. The title complex has a 1D [Cu（bbpy）（H2bptc）]n chain structure, in which the extensive hydrogen-bond interactions make the chain more stable. The neighboring parallel chains are further packed into a 2D layer structure via π···π stacking interaction between the pyridine rings of bbpy ligands. Moreover, the adjacent layers are interconnected by the C–H···π interactions to form a 3D metal-organic framework.

Synthesis and Crystal Structure of an Infinite Sandwich-type Cu(I) Coordination Polymer: {[Cu(abpy)_2](H_3bptc)·(H_2O)}_n Constructed by a Tetracarboxylic Acid

The title compound {[Cu（abpy）2]（H3bptc）·（H2O）}n, an ion-pair complex of [Cu（abpy）2]＋ with [（H3bptc）]- （abpy = 3,3＇-dimethyl-2,2＇-bipyridine and H4bptc = 1,1＇-biphenyl-2,2＇,3,3＇-tetracarboxylic acid）, has been synthesized by a hydrothermal reaction, and its structure was deter- mined by X-ray diffraction and characterized by elemental analysis and IR spectrum. The crystal is of triclinic, space group P1 with a = 8.4955（12）, b = 15.164（2）, c = 15.303（2）, α = 105.704（3）, β = 97.374（3）, γ = 96.764（3）o, CuC40H35N4O9, Mr = 779.26, V = 1857.9（4）3, Dc = 1.393 g/cm3, F（000） = 808, μ = 0.649 mm-1, S = 1.026 and Z = 2. The final R = 0.0493 and wR = 0.1034 for 4026 observed reflections with I 2σ（I）. The copper（I） coordination polymer demonstrates a 3-D sandwich-type structure containing 2-D double H3bptc-chain layers intercalated with the [Cu（abpy）2]＋ layers by extensive hydrogen bonding interactions.

Resolution of 3,3'-Dioxo-1,1'(3H,3(H)spirobi[isobenzofuran] -5,6,5'6'-tetracarboxylic acid and Optically active Polyimides thereof

3,3`-Dioxo-1,1'(3H,3'H)spirobi[isobenzofuran]-5,6,5',6'-tetracarboxylic acid 1 was resolved successfully and the corresponding optically active polyimides PI were synthesized. The properties of the optically active PI and the racemic one were investigated. The results showed that the specific rotation of (-)-PI was about two times to that of the (+)-PI, and the regularity of the optically active PI was higher than that of the racemic one.

Pig Liver Esterase-catalyzed Hydrolysis of Three Diesters of meso-Bicyclic Dicarboxylic Acid and Three Tetraesters of Tetrahydrofuran -2,3,4,5-tetracarboxylic Acid

Three diesters of exo- syn-meso-oxabicyclo (2, 2, 1 ) -hept- 5- ene- 2, 3- dicarboxylic acid and three tetraesters of tetrahydrofuran-2, 3, 4, 5-tetracarboxylic acid were synthesized and tested with enantioselective hydrolysis catalyzed by pig liver esterase(PLE). The results of the PLEcatalyzed hydrolysis were discussed.

Temperature-dependent Syntheses of Two Manganese(Ⅱ) Coordination Compounds Based on an Ether-bridged Tetracarbolylic Acid

0D dinuclear manganese(Ⅱ)coordination compound and 1D chain manganese(Ⅱ)coordination polymer,namely[Mn2(μ-L)(phen)4]·4H2O(1)and{[Mn2(μ5-L)(phen)2]·H2O}n(2),have been constructed hydrothermally using H4L(H4L=2,3,3΄,4΄-diphenyl ether tetracarboxylic acid),phen(phen=1,10-phenanthroline),and manganese chloride at 120 and 160°C,respectively.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses(TGA),and single-crystal X-ray diffraction analyses.Single-crystal X-ray diffraction analyses revealed that two compounds crystallize in the triclinic or monoclinic system,space group P1 or P21/c.Compound 1 discloses a discrete dimeric structure,which is assembled into a 3D supramolecular framework through O-H…O hydrogen bond.Compound 2 has a chain structure.Structural differences between compounds 1 and 2 are attributed to the different reaction temperature.Magnetic studies for compound 2 demonstrate an antiferromagnetic coupling between the adjacent Mn(Ⅱ)centers.

Effect of different metal ions in a new kind of functionalized self-assembled films of trinary complexes on its photoinduced electron transfer property

Three new kinds of self-assembled films were first fabricated through a new strategy. These films have Sn4+, Zr4+ and Ce4+ as bridging central ions, 3, 4, 9, 10-perylene tetracarboxylic acid (PTA) as functional molecules and oxalic acid as connecting ligand. All films were characterized by contact angle, UV spectra, X-ray photoelectron spectra (XPS) and cyclic voltammetry. The effects of light intensity, bias voltage, and electron donor on photocurrents of these films were also studied.

Syntheses,Crystal Structures,Luminescent and Magnetic Properties of Three Ni(Ⅱ),Zn(Ⅱ) and Cd(Ⅱ) Coordination Polymers Based on an Ether-bridged Tetracarboxylic Acid

Two 1D and one 3D coordination polymers,namely[Ni2(μ3-deta)(H2 biim)3(H2O)2]n(1),{[Zn2(μ4-deta)(Phen)2(H2O)]·H2O}n(2)and[Cd2(μ6-deta)(Phen)2(H2O)]n(3),have been constructed hydrothermally using H4deta(H4deta=2,3,3’,4’-diphenyl ether tetracarboxylic acid),H2 biim(H2 biim=2,2’-biimidazole),phen(phen=1,10-phenanthroline),and nickel,zinc or cadmium chlorides at 160℃.The products were isolated as stable crystalline solids and characterized by IR spectra,elemental analyses,thermogravimetric analyses(TGA)and single-crystal X-ray diffraction analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the triclinic system,space group■.Compounds 1 and 2 disclose a 1D chain structure.Compound 3 features a 3D framework.The structural diversity of compounds 1~3 is driven by the metal(Ⅱ)node and the type of supporting ligand.Magnetic studies for compound 1 demonstrate an antiferromagnetic coupling between the adjacent Ni(Ⅱ)centers.The luminescence behavior of compounds 2 and 3 was also investigated.

Synthesis and optoelectronic properties of a novel molecular semiconductor of dithieno[5,6-b:11,12-b']coronene-2,3,8,9-tetracarboxylic tetraester

A facile procedure for the synthesis ofdithieno[5,6-b：11,12-b＇]coronene-2,3,8,9-tetracarboxylic tetra（2- ethylhexyl）ester （DTCTI＇E-EH） from readily available perylene-3,4,9,10-tetracaroboxylic dianhydride is described. The electronic properties of DTCTTE-EH were elucidated on the basis of UV-vis spectra, emission spectrum and electrochemical measurement, which demonstrate that DTCTTE is a new class of components for promising semiconducting materials.

A Highly Selective and Turn-on Fluorescent Probe for Fe^(3+) Ion Based on Perylene Tetracarboxylic Diimide

We have demonstrated a turn-on fluorescent sensor 6 for detection of Fe^(3+) based on photo-induced electron transfer(PET)mechanism.The probe comprises a perylene tetracarboxylic diimide(PDI)fluorophore and two bis((1,2,3-triazol-4-yl)methyl)amine(DTA)moieties as the metal ion receptors.It exhibits high selectivity toward Fe^(3+) over various other metal ions in CH_(3)CN/H_(2)O(1∶1,V/V).The binding stoichiometry for 6-Fe^(3+) complexes has been determined to be 1∶2 by a Job plot of fluorescence.The association constant between 6 and Fe^(3+) was estimated to be 1.04×10^(10)(mol/L)^(−2) by Benesi-Hildebrand equation.