Eight isomorphous metal‐organic frameworks: [Ln2(TATAB)2(H2O)(DMA)6]·5H2O (Ln = Sm ( 1 ), Eu ( 2 ), Gd ( 3 ), Tb ( 4 ), Dy ( 5 ), Er ( 6 ), Tm ( 7 ), Yb ( 8 )); TATAB = 4,4′,4″‐s‐triazine‐1,3,5‐triyl‐p‐aminobenzoate, DMA = N,N‐dimethylacetamide), were synthesized by the self‐assembly of lanthanide ions, TATAB, DMA and H2O. Single‐crystal X‐ray crystallography reveals they are three dimensional frameworks with 2‐fold interpenetration. Solid‐state photoluminescence studies indicate ligand‐to‐metal energy transfer is more efficient for compounds 2 and 4 which exhibit intense characteristic lanthanide emissions at room temperature. 相似文献
Triclinic single crystals of Cu4(H3N–(CH2)9–NH3)(OH)2[C6H2(COO)4]2 · 5H2O were prepared in aqueous solution at 80 °C in the presence of 1,9‐diaminononane. Space group P$\bar{1}$ (no. 2) with a = 1057.5(2), b = 1166.0(2), c = 1576.7(2) pm, α = 106.080(10)°, β = 90.73(2)° and γ = 94.050(10)°. The four crystallographic independent Cu2+ ions are surrounded by five oxygen atoms each with Cu–O distances between 191.4(3) and 231.7(4) pm. The connection between the Cu2+ coordination polyhedra and the [C6H2(COO)4]4– anions yields three‐dimensional framework with negative excess charge and wide centrosymmetric channel‐like voids. These voids extend parallel to [001] with the diagonal of the nearly rectangular cross‐section of approximately 900 pm. The channels of the framework accommodate [H3N–(CH2)9–NH3]2+ cations and water molecules, which are not connected to Cu2+. The nonane‐1,9‐diammonium cations adopt a partial gauche conformation. Thermoanalytical measurements in air show a loss of water of crystallization starting at 90 °C and finishing at approx. 170 °C. The dehydrated compound is stable up to 260 °C followed by an exothermic decomposition yielding copper oxide. 相似文献
Two metal‐organic frameworks, [Zn(dmtrz)(btrc)1/3]n ( 1 ) and [Zn2(dmtrz)2(btec)(H2O)2]n ( 2 ) (dmtrz = 3, 5‐dimethyl‐1‐H‐1, 2,4‐triazole, btrc = 1, 3,5‐benzenetricarboxylate, btec = 1, 2,4, 5‐benzenetetracarboxylate), were synthesized by hydrothermal reaction. The crystal structure analysis reveals that compound 1 is a dense 3D framework with Schläfli symbols of {43}2{46 · 66 · 83}3, which is a loh1 structure. Compound 2 is a 2D network. In addition, the photoluminescence of two compounds were studied in solid state at room temperature, together with their thermal analysis. 相似文献
Two transition metal‐organic coordination polymers, [Mn2(1,3‐bdc)2(Me2bpy)2] · Me2bpy ( 1 ) and [Co(4,4′‐oba)(Me2bpy)] ( 2 ) were hydrothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy, TG, and single‐crystal X‐ray diffraction [1,3‐H2bdc = benzene‐1,3‐dicarboxylic acid, H2oba = 4,4′‐oxybis(benzoic acid) Me2bpy = 4,4′‐dimethyl‐2,2′‐bipyridine]. Compound 1 crystallizes in the orthorhombic system, space group P212121, with a = 23.371(5), b = 14.419(3), and c = 14.251(3) Å. Compound 2 crystallizes in the monoclinic system, space group P21/c, with a = 7.4863(15), b = 18.272(4), c = 16.953(5) Å, and β = 107.44(3)°. The crystal structure of complex 1 is a wave‐like layer with central Mn2+ atoms bridged by 1,3‐bdc ligands, whereas the structure of compound 2 presents a ladder chain of hexacoordinate Co2+ atoms, in which the metal atoms are bridged by 4,4′‐oba ligands and decorated by Me2bpy ligands. The two compounds are further extended into 3D supramolecular structures through π–π stacking interactions. Additionally, the compounds show intense fluorescence in solid state at room temperature. 相似文献
Four new metal‐organic frameworks [Cu2(2,2′‐bipy)2(ox)(H2O)2]·(H2bptc) ( 1 ), [Cu(bptc)0.5(phen)(H2O)]·H2O ( 2 ), Co2(bptc)(bmb)1.5 ( 3 ) and [Cd2(bptc) (bmb)]·3H2O ( 4 ) (H4bptc = 3,3′,4,4′‐biphenyltetracarboxylic acid, ox = oxalate, phen = 1,10‐phenanthroline, 2,2′‐bipy = 2,2′‐bipyridine and bmb = 4,4′‐bis((1H‐imidazol‐1‐yl)methyl)biphenyl), were obtained by reactions of the corresponding metal salts with H4bptc and N‐containing auxiliary ligands and their structures were determined by single‐crystal X‐ray diffraction. The results reveal that 1 has a 0‐D structure consisting of discrete ionic entities, while 2 features a 1‐D ladder structure. Additionally, there exist π‐π stacking and intermolecular hydrogen‐bonding interactions in 1 and 2 , respectively, forming 3‐D supramolecular structures. In 3 ‐ 4 , undulating 2‐D metal‐bptc layer structures are formed with two different coordination modes of bptc carboxylate groups, respectively, which are further extended by bmb into 3‐D structures. Magnetic properties of 1 and 3 have been studied. The photoluminescence property of 4 has also been investigated. Moreover, nonlinear optical measurements showed that 4 displayed a second‐harmonic‐generation (SHG) response of 0.7 times of that for urea. 相似文献
The 2D CuII metal‐organic framework [Cu2(bptc)(H2O)4]n · 4nH2O ( 1 ) (H4bptc = biphenyl‐2,2′,4,4′‐tetracarboxylic acid) was hydrothermally synthesized and characterized by single‐crystal X‐ray diffraction and magnetic measurements. In the structure, bptc4– serves as a twisted Π‐shaped organic building block to connect paddlewheel [Cu2(COO)4] dinuclear units and mononuclear units through 2‐/2′‐carboxylate and 4‐/4′‐carboxylate, respectively. According to the magnetic analysis using a dimer‐plus‐monomer model, strong antiferromagnetic coupling is operative within the dinuclear unit (J = –311 cm–1 based on H = –J S 1 S 2), and the compound behaves like a mononuclear molecule at low temperature. 相似文献
A metal‐organic framework (MOF ) formulated as [Cd2(μ3‐L)2(DMF )4]•H2O ( CdL ) [H2L =9‐(pyridin‐4‐yl)‐ 9H ‐carbazole‐3,6‐dicarboxylic acid, DMF =N ,N ‐dimethylformamide] was synthesized under solvothermal condition. Crystal structural analysis reveals that CdL features the layered 2D framework with L2− ligands as 3‐connected nodes. The compound CdL emits blue‐violet light with the narrow emission peak and the emission maximum at 414 nm upon excitation at the maximum excitation wavelength of 340 nm. The compound CdL has a similar emission spectrum curve to the free H2L ligand that indicates the emission of compound CdL should be originated from the coordinated L2− ligands. 相似文献
A series of π‐extended aromatic indenofluorene (IF) analogues with naphthalene and anthracene cores have been synthesized through acid‐catalyzed intramolecular cyclization. The regioselectivity of the reaction is controlled by a combination of steric and electronic factors and in some cases several possible regioisomers have resulted from the same precursor. The effects of ring connectivity on the optoelectronic properties were investigated by DFT calculations, absorption/emission spectroscopy, cyclic voltammetry, and spectroelectrochemical studies. All regioisomers exhibited a redshift of their absorption/emission bands relative to the parent IF analogues, but the magnitude of this shift and other optoelectronic properties (luminescence quantum yield, etc.) depends on the ring connectivity in a less obvious manner. 相似文献
Four metal‐organic frameworks (MOFs), {[Mn3.5L(OH)(HCOO)4(DMF)] · H2O} ( 1 ), {[In2.5L2O(OH)1.5(H2O)2] · DMF · CH3CN · 2H2O} ( 2 ), {[Pb4L3O(DMA)] · CH3CN} ( 3 ), and {[LaL(NO3)(DMF)2] · 2H2O} ( 4 ) were synthesized by utilizing the ligand 2,2′,6,6′‐tetramethoxy‐4,4′‐biphenyldicarboxylic acid (H2L) via solvothermal methods. All MOFs were characterized by single‐crystal X‐ray diffraction, powder X‐ray diffraction, thermogravimetric analysis, and infrared spectroscopy. In 1 , the Mn2+ ions are interconnected by formic groups in situ produced via DMF decomposition to form a rare 2D macrocyclic plane, which is further linked by L2– to construct the final 3D network. In 2 , 1D zip‐like infinite chain is formed and then interconnected to build the 3D framework. In 3 , a [Pb6(μ4‐O)2(O2C)10(DMA)2] cluster with a centrosymmetric [Pb6(μ4‐O)2]8+ octahedral core is formed in the 3D structure. In 4 , the La3+ ions are connected with each other through carboxylate groups of L2– to generate 1D zigzag chain, which is further linked by L2– to construct a 3D network with sra topology. Solid photoluminescence properties of 3 and 4 were also investigated. 相似文献
Cyclocondensation of polystyrene‐supported α‐selenopropionic acid with amidoximes in the presence of 1‐(3‐dimethylaminopropyl)‐3‐ethylcarbodiimide hydrochloride (EDC) followed by oxidative deselenation efficiently afforded 5‐vinyl 1,2,4‐oxadiazoles in good yield and purity with a facile work‐up procedure. 相似文献
The new MOF Ga‐MIL‐53‐PDA [Ga(OH)(O2C‐C8H8‐CO2)] · H2O ( 1 ) was synthesized by a hydrothermal reaction of gallium nitrate, 1,4‐phenylenediacetic acid (H2PDA) and sodium hydroxide at 100 °C for 24 h. The product is a structural analogue of the archetypical MIL‐53 framework. Its crystal structure was determined by Rietveld refinement of powder X‐ray diffraction (PXRD) data. Furthermore 1,4‐phenylenedipropionic acid (H2PDP) was employed for further synthesis, which resulted in the dense layered coordination polymers [Ga2(OH)4(O2C‐C10H12‐CO2)] ( 2 ) and [Ga(OH)(O2C‐C10H12‐CO2)] ( 3 ), for which accurate structural models could be established. All compounds were fully characterized and tested regarding potential breathing behavior. Most remarkably, Ga‐MIL‐53‐PDA showed a subtle flexibility upon de/‐rehydration also confirming its porosity, but no drastic structural changes were observed. 相似文献
A new inorganic–organic hybrid zinc phosphite, [Zn(HPO3)(C6H11NO2)]n, has been synthesized hydrothermally. Protonated piperidin‐1‐ium‐4‐carboxylate (PDCA) was generated in situ by hydrolysis of the piperidine‐4‐carboxamide precursor. The P atom possesses a typical PO3H pseudo‐pyramidal geometry. The crystal structure features an unusual (3,4)‐connected two‐dimensional inorganic zinc–phosphite layer, with organic PDCA ligands appended to the sheets and protruding into the interlayer region. Helical chains of opposite chirality are involved in the construction of a puckered sheet structure. 相似文献
Yes, HIMs can! A series of 2,3,6,7‐tetraarylbenzo[1,2‐b:4,5‐b′]dipyrroles (BDPs) were synthesized using zinc‐mediated double cyclization. Organic light‐emitting diodes consisting of BDP:PPB as a hole‐injection layer could be driven at a lower voltage than a PEDOT:PSS‐based device. Correlation of the IP values with the driving voltage shed some light on the mechanism of hole‐injection processes.
Three new complexes: [M(L)(H2O)] [M = Zn ( 1 ), Co ( 2 ), Ni ( 3 ); H2L = 5‐(pyridin‐2‐ylmethyl)aminoisophthalic acid] were synthesized under hydrothermal conditions at 180 °C and were characterized by elemental analysis, FT‐IR spectroscopy, single‐crystal X‐ray diffraction, and thermogravimetric analysis (TGA). The results of X‐ray diffraction analysis reveal that complexes 1 – 3 are isostructural and crystallize in the monoclinic system with space group P21/c. Each of the complexes displays a (3,3′)‐connected two‐dimensional (2D) wave‐like network with (4,82) topology, within which five‐membered uncoplanar N,N‐chelated metallacycles are shaped. Delicate N–H ··· O and O–H ··· O hydrogen bonding interactions exist in complexes 1 – 3 . Adjacent 2D layers are linked by intermolecular interactions, resulting in the construction of extended metal‐organic frameworks (MOFs) in complexes 1 and 2 . 相似文献
Treatment of lithio derivativ
e of novel PEG-supported a-phenylselenopropionate with aldehydes, followed by oxidation-elimination with 30% hydrogen peroxide, formed Baylis-Hillman products, which were then reacted with sodium arylsulfinate. The resulting sulfonylated products were cleaved from the PEG efficiently affording methyl (2Z)-2-arylsulfonylmethyl-2-alkenoates in good yields and high purities. 相似文献