Syntheses,structures,and properties of three coordination polymers based on 5⁃ethylpyridine⁃2,3⁃dicarboxylic acid and N⁃containing ligands

Three coordination polymers[Mn(epda)(2,2'⁃bipy)(H_(2)O)](1),[Mn(epda)(phen)](2),and[Co_(2)(epda)2(bpe)2(H_(2)O)_(4)]·5H_(2)O(3)(H2epda=5⁃ethyl⁃pyridine⁃2,3⁃dicarboxylic acid,2,2'⁃bipy=2,2'⁃bipyridine,phen=phenanthroline,bpe=1,2⁃bis(4⁃pyridyl)ethylene)were synthesized by solvothermal reactions and characterized by single⁃crystal X⁃ray diffraction,thermogravimetric analyses,IR spectroscopy and elemental analysis.1 displays a 1D chain struc⁃ture,and these chains are joined by O-H…O hydrogen bonding andπ⁃πstacking interactions to generate a 2D layer structure.2 displays a 2D layer structure,and adjacent layers are generated 3D architecture throughπ⁃πstacking interactions.3 displays a 1D chain structure,and adjacent chains are generated double layer structure through O-H…O hydrogen bonding.The fluorescent properties of 1 and 3 indicate that they can potentially be used as a luminescent sensor.1 was highly selective and sensitive towards o⁃nitrophenol through different detection mechanisms,however,3 was highly selective and sensitive towards 2,4,6⁃trinitrophenol.In addition,the magnetic behavior of 2 has also been investigated.CCDC:2172533,1,2355773,2,2355774,3.

A Novel 3D Cd-based Luminescence Metal-organic Framework: Synthesis, Structure and Luminescent Sensing Properties

A three-dimensional(3 D) Cd-based metal-organic framework(MOF), [Cd(H2 O)(PAA)]·(H2 O)2(complex 1) has been rationally designed and synthesized by using 4-(pyrimidin-5-yl)isophthalic acid(H2 PAA) and Cd(NO3)2·4 H2 O under solvothermal conditions. The structure has been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction(PXRD) and thermogravimetric analyses(TGA). Single-crystal X-ray diffraction analyses reveal that complex 1 consists of a 3 D network with one-dimensional(1 D) channels. Moreover, 1 exhibits strong luminescent emission in solid state at room temperature. Fluorescence quenching was observed when treating complex 1 with picric acid(PA), 2,4-dinitrophenylhydrazine(2,4-DNPH) and p-nitroaniline(p-NA), revealing that the as-synthesized complex could be used as a luminescence sensor for the detection of PA, 2,4-DNPH and p-NA.

Two Zinc Complexes Supported by in situ Formed Etheric Ligands

Two zinc complexes, [Zn(MPIP)Cl2](1) and [Zn(EPIP)Cl2](2), where MPIP = 1-(methoxymethyl)-3-(pyridin-2-yl)imidazo[1,5-a]pyridine and EPIP = 1-(ethoxymethyl)-3-(pyridin-2-yl)imidazo[1,5-a]pyridine, were synthesized under solvothermal conditions. The etheric ligand MPIP was formed in situ via metal ligand reaction between(3-(pyridin-2-yl)imidazo[1,5-a]pyridin-1-yl)methanol(HPIPM) and methanol solvent. Similarly, the ligand EPIP was generated in situ from the reaction of HPIPM with ethanol solvent. The structures of 1 and 2 were characterized by X-ray single-crystal diffraction analysis. They are four-coordinated mononuclear complexes, and the ZnII ion of 1 and 2 displays distorted tetrahedral geometry. The photoluminescent properties of 1 and 2 were investigated. Strong emissions were observed for both 1 and 2, which were ascribed as the intraligand(π-π*) fluorescent transitions. This paper provides a simple and efficient method for the synthesis of etheric compounds.

A Zinc(Ⅱ) Coordination Polymer Based on a Polycarboxylate Ligand: Synthesis, Crystal Structure, Photoluminescence and Photocatalysis

A new zinc coordination polymer（CP） {[Zn1.5（ttb）0.5（phen）（H2O）]·2 H2O}n（1）,（H6ttb = 3,4,5-tricarboxyl-（3?,4?,5?-tricarboxylazophenyl）benzene, phen = 1,10-phenanthroline）, has been hydrothermally synthesized and structurally characterized by single-crystal X-ray determination, IR and thermogravimetric analysis（TGA）. CP 1 crystallizes in the monoclinic system, space group C2/c with a = 12.402（3）, b = 15.231（3）, c = 22.233（4） ?, β = 94.388（3）°, Zn1.5C21H16N3O9, Mr = 552.42, V = 4187.3（15） ?3, Dc = 1.753 g/cm3, F（000） = 2240, μ = 1.795 mm-1, S = 1.041, GOF = 1.041, Rint = 0.0169, 2.36°<θ<30.95°, and Z = 8. The final refinement gave R = 0.0340 and w R = 0.0927 for 5791 observed reflections with I > 2σ（I）. The completely deprotonated（ttb）6- ion in 1 adopts an octadentate coordination mode（μ8-η2-η1-η1-η1-η1-η2）. Four of the carboxyl groups are coordinated with four zinc ions by monodentate, respectively. While the other two carboxyl groups are coordinated with four zinc ions by bidentate, respectively. So, CP 1 possesses a 3 D network structure cross-linked by（ttb）6-ion. The XRD, UV and photoluminescence properties of CP 1 were also studied. Remarkably, 1 exhibits photocatalytic activities for the degradation of dye（MO） under UV light irradiation and shows good stabilities towards UV-light photocatalysis.

Chemoselective Transfer Hydrogenation of Nitroarenes with Ammonia Borane Catalyzed by Copper N-Heterocyclic Carbene Complexes

Herein,we present a method for the homogeneous hydrogenation of nitroarenes to produce anilines using low catalyst loading(1 mo%)of copper N-heterocyclic carbene complexes as the catalyst and ammonia borane as the source of hydrogen.A wide range of nitroarenes,featuring diverse functional groups,were selectively transformed into their corresponding primary aromatic amines with high yields.This process can be readily scaled up and exhibits compatibility with various sensitive functional groups,including halogen,trifluoromethyl,aminomethyl,alkenyl,cyano,ester,amide,and hydroxyl.Notably,this catalytic methodology finds application in the synthesis of essential drug compounds.Mechanistic investigations suggest that the in-situ-generated Cu-H species may serve as active intermediates,with reduction pathways involving species such as azobenzene,1,2-diphenylhydrazine,nitrosobenzene,and N-phenylhydroxylamine.

A Novel 3D Zn-based Luminescence Metal-organic Framework: Synthesis, Structure and Fluorescence Enhanced Sensing of Ammonia Vapor in Air

A three-dimensional(3D)zinc metal-organic framework(MOF),Zn4(μ4-O)(bcd)3(complex 1)has been synthesized by using 1-[bis(4-carboxylphenyl)methyl]-1,3-diazole(H2 bcd)and Zn(NO3)2·6 H2O under hydrothermal conditions.The structure has been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses,IR spectra,powder X-ray diffraction(PXRD)and thermogravimetric analyses(TGA).Single-crystal X-ray diffraction analyses reveal that complex 1 crystallizes in trigonal system,space group R3 with a=23.0521(6),b=23.0521(6),c=15.3326(6)A,γ=120°,V=7056.2(4)A^3,Z=6,C54H36N6O13Zn4,Mr=1242.37,Dc=1.754 g/cm^3,F(000)=3756,the final R=0.0411 and wR=0.1007 for 2743 observed reflections(I>2σ(I)).Complex 1 consists of a 3D network constructed by four nuclear clusters Zn4(μ4-O)(COO)6 N3 and the bcd2-ligand.Interestingly,1 exhibits strong luminescent emission in solid state at room temperature and could be used as a qualitative fluorescence enhancing sensor for ammonia vapor in air.

Two Co(Ⅱ)Complexes Constructed from 1-(3,5-Dicarboxybenzyl)-3,5-pyrazole Dicarboxylic Acid:Syntheses,Structures and Magnetic Properties

Two new complexes[Co_(2)(L)(4,4´-bip)(H_(2)O)_(3)]_(n)(1)and{[Co(L´)_(2)(phen)]·2H_(2)O)}_(n)(2)(H_(4)L=1-(3,5-dicarboxybenzyl)-3,5-pyrazole dicarboxylic acid,H_(3)L´=1-(3,5-dicarboxybenzyl)-3-pyrazole carboxylic acid,4,4´-bip=4,4´-bis(1-imidazolyl)biphenyl,phen=1,10-phenanthroline)were synthesized.Complexes 1 and 2 have been characterized by IR spectrography,X-ray single-crystal diffraction,elemental analysis and thermogravimetry.1 crystallizes in monoclinic system,space group P2_(1/c).Complex 2 crystallizes in monoclinic system,space group I2/a.It is remarkable that in situ hydrothermal decarboxylation was observed during preparing complex 2.In addition,magnetic analysis indicates that antiferromagnetic interaction exists among Co(Ⅱ)ions in complexes 1 and 2.