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1.
A new Pebax-based mixed matrix membrane with amide functionalized PCP filler shows promising CO2/N2 separation at ambient temperature.  相似文献   

2.
A new dynamic porous coordination polymer (PCP) [Ni(dcpy)(bipy)(0.5)(H(2)O)]·1.5H(2)O (1) was synthesized by assembly of 3-(2',5'-dicarboxylphenyl)pyridine (dcpy), 4,4'-bipyridine (bipy) and NiSO(4)via solvothermal, hydrothermal and microwave methods, displaying a wavelike 2D stacked layer framework. Gas adsorption studies for 1 shows a high selective adsorption of CO(2) over other gases (N(2), CH(4) and CO). The adsorption capacity for N(2) can be moderately altered by different activation temperatures demonstrating the framework flexibility of 1.  相似文献   

3.
Four porous crystalline coordination polymers with two-dimensional frameworks of a double-edged axe-shaped motif, [[Co(NCS)(2)(3-pia)(2)] x 2 EtOH.11 H(2)O](n) (1 a), [[Co(NCS)(2)(3-pia)(2)] x 4 Me(2)CO](n) (3 a), [[Co(NCS)(2)(3-pia)(2)] x 4T HF](n) (3 b) and [[Co(NCS)(2)(3-pna)(2)](n)] (5), have been synthesized by the reaction of cobalt(II) thiocyanate with N-(3-pyridyl)isonicotinamide (3-pia) or N-(3-pyridyl)nicotinamide (3-pna). X-ray crystallographic characterization reveals that adjacent layers are stacked such that channels are created, except in 5. The channels form a hydrogen-bonded interior for guest molecules; in practice, 1 a contains ethanol and water molecules as guests in the channels with hydrogen bonds, whereas 3 b (3 a) contains tetrahydrofuran (acetone) molecules. In 1 a, the "double-edged axe-shaped" motifs in adjacent sheets are not located over the top of each other, while the motifs in 3 b stack so perfectly as to overlap each other in an edge-to-edge fashion. This subtle change in the three-dimensional framework is associated with the template effect of the guests. Compound 5 has no guest molecules and, therefore, the amide groups in one sheet are used for hydrogen-bonding links with adjacent sheets. Removal of the guest molecules from 1 a and 3 b (3 a) causes a structural conversion accompanied by a color change. Pink 1 a cannot retain its original framework and changes into a blue amorphous compound. On the other hand, the framework of pink 3 b (3 a) is transformed to a new crystalline framework of violet 4. Interestingly, 4 reverts to the original pink crystals of 3 b (3 a) when it is exposed to THF (or acetone) vapor. Spectroscopic measurements (visible, EPR, and IR) provide a clue to the crystal-to-crystal transformation; on removal of the guests, the amide groups are used to form the beta sheet-type hydrogen bonding between the sheets, and thus the framework withstands significant stress on removal of guest molecules. This mechanism is attributed to the arrangement of the adjacent sheets so suited in regularity that the beta sheet-type structure forms efficiently. The apohost 4 does not adsorb cyclopentane, showing a guest selectivity that, in addition to size, hydrogen-bonding capability is required for the guest molecules. The obtained compound is categorized as a member of a new generation of compounds tending towards functional porous coordination polymers.  相似文献   

4.
Photochemical [2+2] cycloaddition reactions in a two-dimensional interdigitated porous crystalline framework proceed in a single-crystal-to-single-crystal manner, and one-dimensional channels show structural changes that have a significant impact on the CO(2) sorption.  相似文献   

5.
The hydrothermal reaction of MnSO4 with the achiral 2-carboxyethyl(phenyl)phosphinate ligand (H2L) afforded a 2?D coordination polymer manganese phosphinate, [Mn(HL)2]n (1) (H2L?=?2-carboxyethyl(phenyl) phosphinic acid). It contains two types of dimeric ring motifs, which can generate a layer structure through edge-sharing. The interlayer stacking by C-H…π interactions between the C-H groups of the phenyl rings of HL- and the phenyl rings of the adjacent layers results in its crystallization in a noncentrosymmetric crystal structure with (43)2(46·66·83) topology. Compound 1 shows a second harmonic generation response that is 0.8 times that of urea. The luminescence spectrum indicates an emission maximum at 457?nm, attributed to an intra-ligand emission state.  相似文献   

6.
Benzene vapor sorption by the organometallic coordination polymer [Zn2(bdc)2(dabco)] (H2bdc = benzene-1,4-dicarboxylic acid, dabco = diazabicyclo[2.2.2]octane) is reported. The [Zn2(bdc)2(dabco)] polymer has a high C6H6 sorption capacity of up to 3.8 mol of benzene per formula unit. The heat of sorption has been determined, and its dependence on the composition of the inclusion compound has been investigated. Included benzene molecules are nonequivalent in terms of the energy of their interaction with the metal-organic framework.  相似文献   

7.
8.
Journal of Thermal Analysis and Calorimetry - The adsorption of Pt(IV) by iron oxide (Fe3O4) superparamagnetic nanoparticles (SPION) functionalized with 3-mercaptopropionic acid (3-MPA) is...  相似文献   

9.
Hydrophobic ethyl, butyl or hexyl groups were introduced into the dicarboxylate ligand in the fluorescent porous coordination framework [Zn_2(fda)_2(bpy)](LMOF-202, H_2fda=9H-fluorene-2,7-dicarboxylic acid, bpy=4,4′-bipyridine) for improving water stability and tuning oxygen sensitivity. The long hexyl groups gave satisfactory water stability but its oxygen sensitivity is low(70.8% fluorescence quenched at 1 bar O_2(1 bar=105 Pa)). In contrast, the shorter side groups gave high oxygen sensitivity(93.9% fluorescence quenched at 1 bar O_2) and low water stability. The derivation of the Stern-Volmer curves of the O_2 luminescence quenching data from the linear form can be used for detecting trace impurities in the luminescent framework, being much more sensitive than conventional methods such as powder X-ray diffraction. Mixing the ethyl and hexyl groups in the solid-solution manner brought high oxygen sensitivity(96.4% fluorescence quenched at 1 bar O_2) and high water stability simultaneously in the same coordination framework.  相似文献   

10.
A homochiral luminescent porous coordination polymer, [Cd(L)(H(2)O)]·3H(2)O, with interconnected collagen like triple-helical chains has been synthesized solvothermally by using cadmium(II) salt and a newly designed d-isosorbide-based, enantiomerically pure chiral ligand. The framework is a 2D porous material and forms a 1D channel along the a axis, with the channel dimensions ~6.2 × 4.4 ?(2). The compound has high selectivity in the uptake of water and methanol over other solvents (e.g., tetrahydrofuran, ethanol, benzene, and cyclohexane) inside the channels.  相似文献   

11.
We designed a novel ditopic bisterpyridyl ligand containing o-carborane that can construct a coordination polymer by complexation with metal ions. Through the use of Sonogashira-Hagihara coupling, the desired ligand molecule was successfully synthesized. Addition of Zn(II) ions rapidly underwent the generation of a fluorescent coordination polymer, which was confirmed by (1)H NMR, UV-vis, and fluorescent titration experiments. Furthermore, the electronic structure of the bisterpyridyl ligand molecules was drastically changed upon the complexation with metal ions. The obtained coordination polymer showed light blue emission derived from the intraligand charge transfer (ILCT) state, whereas a bare ligand molecule exhibited yellowish-green aggregation-induced emission (AIE) in a poor solvent such as water, because of the variable C-C bond in o-carborane.  相似文献   

12.
A two-dimensional coordination polymer, [Mn(Enox)2]·4H2O, 1 (H-Enox?=?1-ethyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-pierazinyl)-1,8-naphtyridine-3-carboxylic acid), has been rationally designed and synthesized under hydrothermal conditions. Compound 1 is self-assembled from bifunctional drug ligand enoxacin and transition metal ion Mn(II) through covalent coordination bonds and hydrogen bondings.  相似文献   

13.
14.
Five-coordinate gallium and aluminium dihydrides, H2Ga[N(CH2CH2NMe2)2] () and H2Al[N(CH2CH2NMe2)2] (), were synthesized and found to be volatile and thermally stable. and reacted with H3Ga(NMe3) and H3Al(NMe3), respectively, to form H2Ga[N(CH2CH2NMe2)2]GaH3 () and H2Al[N(CH2CH2NMe2)2]AlH3 (), in which the amido nitrogen bridged between the MH2 and MH3 groups (M=Ga or Al). A mixed metal complex, H2Al[N(CH2CH2NMe2)2]GaH3 () was obtained from the reaction of with H3Al(NMe3) or with H3Ga(NMe3), and a crystal consisting of a mixture of and was structurally characterized. The five-coordinate chloro derivative, Cl2Ga[N(CH2CH2NMe2)2] (), was synthesized and characterized.  相似文献   

15.
Two novel temperature-controlled supramolecular stereoisomers of porous copper coordination networks have been synthesized and characterized.  相似文献   

16.
A new strategy to synthesize monodispersed porous coordination polymer (PCP) nanocrystals at room temperature was developed and utilized for the formation of PCP thin films on gold substrates with fine control over the crystal sizes using the coordination modulation method. Hybridization of these PCP thin films with an environment-controlled quartz crystal microbalance system allowed determining the adsorption properties for organic vapors (methanol and hexane). In the case of high sensitivity (at the low-concentration dosing of analytes), the sensor response depended on the crystal size but not on the type of analyte. In contrast, at the high-concentration dosing, a clear dependence of the sorption kinetics on the analyte was observed due to significant sorbate-sorbate interaction.  相似文献   

17.
This work describes the development of a new tridentate ligand effective for the asymmetric catalysis of Nozaki-Hiyama allylation and methallylation. Various aldehydes were allylated or methallylated with good enantioselectivity (86-96%), and a key intermediate of calcitriol lactone synthesis was also obtained with excellent diastereoselectivity (97% de, 91%). The enantioselective reaction catalyzed by this Cr-ligand complex is applicable to a broad range of aldehydes and has great potential for natural product synthesis. Another remarkable feature of this ligand is the stability of the Cr-ligand complex which was recovered after the enantioselective reaction and recycled twice without diminishing the enantioselectivity and yield.  相似文献   

18.
A novel porous coordination polymer, Cu(II)(mtpm)Cl(2) [mtpm = tetrakis(m-pyridyloxy methylene)methane], has been synthesized, and its crystal structure has been determined. Its adsorption isotherms for water, methanol, and ethanol are totally different from each other. It adsorbs water at low humidity and shows gate-open behavior for methanol, but it does not adsorb ethanol. This compound has the capacity to separate both methanol and water from bioethanol, which is a mixture of water, methanol, and ethanol.  相似文献   

19.
The disodium salt of a bis(aryloxide)-N-heterocyclic-carbene dianionic ligand, Na2[L], was prepared by reaction of 1,3-bis(4,6-di-tert-butyl-2-hydroxybenzyl)imidazolium bromide [H3L]Br with 3 equiv. of NaN(SiMe3)2. Reaction of ZrCl4(thf)2 with 1 equiv. of Na2[L] gave a mixture of [L]ZrCl2(thf) (1) and [L]2Zr (2). When the amount of Na2[L] was increased to 2 equiv., the bis(bis(aryloxide)-N-heterocyclic-carbene) complex 2 was obtained in good yield. The dichloro complex 1 is a precursor to organometallic derivatives, and treatment with PhCH2MgCl or Me3SiCH2Li yielded [L]ZrR2 [R = CH2Ph (3), CH2SiMe3 (4)]. The disodium salt of the ligand Na2[L] is unstable and undergoes 1,2-benzyl migration, whereas zirconium complexes of the [L]2− ligand are found to be thermally stable in solid and solution. The X-ray crystal structures of 1, 2, and 3 are described.  相似文献   

20.
A new 2D pillared-bilayer porous coordination polymer (PCP) has been synthesized and structurally characterized that shows selective adsorption of CO(2) over other gases (N(2), O(2), Ar, H(2), CH(4)) and guest selective single/double-step adsorption of vapor correlated to the successive confinement of adsorbates in a 1D channel and a 2D interlayer space.  相似文献   

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