35 research outputs found
A Robust Titanium Isophthalate Metal-Organic Framework for Visible-Light Photocatalytic CO2 Methanation
[EN] Isophthalic acid (IPA) has been considered to build metal-organic frameworks (MOFs), owing to its facile availability, unique connection angle-mode, and a wide range of functional groups attached. Constructing titanium-IPA frameworks that possess photoresponse properties is an alluring characteristic with respect to the challenge of synthesizing new titanium-based MOFs (Ti-MOFs) Here, we report the first Ti-IPA MOF (MIP-208) that efficiently combines the use of preformed Ti-8 oxoclusters and in situ acetylation of the 5-NH2-IPA linker. The mixed solid-solution linkers strategy was successfully applied, resulting in a series of multivariate MIP-208 structures with tunable chemical environments and sizable porosity. MIP-208 shows the best result among the pure MOF catalysts for the photocatalytic methanation of carbon dioxide. To improve the photocatalytic performance, ruthenium oxide nanoparticles were photo-deposited on MIP-208, forming a highly active and selective composite catalyst, MIP-208@RuOx, which features a notable visible-light response coupled with excellent stability and recycling ability.S.W. acknowledges the support from the National Natural Science Foundation of China (22071234) and the Fundamental Research Funds for the Central Universities (WK2480000007). S.N. thanks the Ministerio de Ciencia, Innovacion y Universidades (RTI2018-099482-A-I00 project, the Fundacion Ramon Areces (XVIII Concurso Nacional para la Adjudicacion de Ayudas a la Investigacion en Ciencias de la Vida y de la Materia, 2016), and Generalitat Valenciana grupos de investigacion consolidables (AICO/2019/214 project) and Agencia Valenciana de la Innovacion (INNEST/2020/111 project) for financial support. C.-C.C. acknowledges the support from the Program of China Scholarship Council (201700260093) and PHC Cai YuanPei Project (38893VJ). C.M.-C. is grateful for financial support from the Institut Universitaire de France (IUF) and the Paris Ile-de-France Region -DIM "Respore.'' H.G. thanks the Spanish Ministry of Science and Innovation (Severo Ochoa and RTI2018-098237-CO2-1) and Generalitat Valenciana (Prometeo2017/083) for financial support. The authors thank the staff at Synchrotron SOLEIL and the associated scientists for beamtime and assistance during SCXRD data collections on PROXIMA 2A, as well as Dr. Peng Guo and Dr. Nana Yan from Dalian Institute of Chemical Physics (Chinese Academy of Sciences) for the collection of high-resolution PXRD data for Rietveld refinement.Wang, S.; Cabrero-Antonino, M.; Navalón Oltra, S.; Cao, C.; Tissot, A.; Dovgaliuk, I.; Marrot, J.... (2020). A Robust Titanium Isophthalate Metal-Organic Framework for Visible-Light Photocatalytic CO2 Methanation. 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First Keto-Functionalized Microporous Al-Based Metal–Organic Framework:
A new microporous aluminum MOF is reported, which is based on the interconnection of infinite chains of trans-connected AlO6-polyhedra via 4,4′-benzophenonedicarboxylate ions. The framework exhibits nonintersecting channels with a diameter of 8 Å running along the a- and the b-axis. These channels are easily accessible for gas molecules, and the implementation of a keto-group into this MOF makes it an attractive candidate for postsynthetic modification reactions. A careful topological analysis showed that the underlying topology of the framework is based on a tetragonal homogeneous sphere packing
MIL-103, A 3-D Lanthanide-Based Metal Organic Framework with Large One-Dimensional Tunnels and A High Surface Area
Structural Studies of Large dsDNA Viruses using Single Particle Methods
Structural studies of large biological assemblies pose a unique problem due to their size, complexity and heterogeneity. Conventional methods like x-ray crystallography, NMR, etc. are limited in their ability to address these issues. To overcome some of these limitations, single particle methods were used. In these methods, each particle image is manipulated individually to find the best possible set of images to reconstruct the 3D structure. The structural studies in this thesis, exploit the advantages of single particle methods. The large data set generated by the SPI study of PR772 provides better statistics about the sample quality due to the use of GDVN, a container-free sample delivery method. By analyzing the diffusion map, we see that the use of GDVNs as a sample delivery method produces wide range of particle sizes owing to the large droplet that are created. The high-resolution structure of bacteriophage PR772 confirmed the speculation about the heteropentameric nature of the penton and revealed the new architecture of the vertex complex consisting of a hetero-pentameric penton formed with three copies of P5 and two copies of P31. The beta propeller region of P2, formed by domains I and II is bound to the N-terminal domain of P5. The structure also reveals new conformations of N-terminal and C-terminal region of P3 which play an important role in particle assembly and structural stability. The study of Melbournevirus revealed the protein composition in a packed particle. The CryoEM structure of Melbournevirus reveals a T=309 capsid with an inner lipid membrane. A dense body was found in the viral particle, a feature not observed in other viruses of the Marseilleviridae family. The density of this body is similar to a nucleic acid-protein complex. This observation, along with the histone-like protein identified during study, suggest genome organization in the viral particle, similar to higher organisms. The soft X-ray microscope operated in the water-window shows the progression of the Cedratvirus lurbo infection in the host cell without the use of chemical fixation, staining, sample dehydration or polymer embedding. The study revealed a significant bioconversion from the host cell to the viral particle at later stages of infection
Synthesis and fluorosolvatochromic properties of 1,7-annulated indoles
A new family of indole-based fluorescent dyes has been easily synthesized from readily available substrates. The structures of all new compounds were confirmed by NMR, IR, and HRMS and a crystallographic structure has been obtained for the 2,6-dicyanoaniline derivative 3. UV/vis absorption and photoluminescence spectroscopy analyses were performed on push-pull indole derivatives 1, 2 and 4. While the absorption maxima were almost independent of the solvent, the emission energy decreased while increasing the solvent polarity. A linear correlation between the orientation polarizability (Delta f) of the solvent and the Stokes shifts was observed and DFT calculations were carried out to study the influence of the planarity of the structures on the fluorescent quantum yields
Structural and photoluminescent studies of non-centrosymmetric manganese(II) N-(2-pyridylmethyl)-(L)-alanine) dicyanamide
The dinuclear compound, [Mn2(Pyala)2(Dca)2(H2O)]n·2H2O (1) (Pyala = N-(2-pyridylmethyl)-L-alanine and Dca = dicyanamide anion) has been synthesized and characterized by elemental analysis, IR and single crystal X-ray diffraction techniques. The crystal data for C22H26Mn2N10O6: orthorhombic, space group P212121 (no. 19), a = 10.3728(8) Å, b = 15.9780(12) Å, c = 16.3585(13) Å, V = 2711.2(4) Å3, Z = 4, T = 198(2) K, μ(MoKα) = 0.989 mm-1, Dcalc = 1.559 g/cm3, 129607 reflections measured (3.564° ≤ 2Θ ≤ 60.046°), 7923 unique (Rint = 0.0324, Rsigma = 0.0155) which were used in all calculations. The final R1 was 0.0169 (I > 2σ(I)) and wR2 was 0.0458 (all data). The obtained non-centrosymmetric dinuclear Mn(II) complex contains two unique Mn(II) cations with similar octahedral coordination environment. Photoluminescent measurements on the complex in the solid state show that it displays strong photoluminescence at 442 nm
Structural and magnetic properties of MnIII and CuII tetranuclear azido polyoxometalate complexes: multifrequency high-field EPR spectroscopy of Cu4 clusters with S = 1 and S = 2 ground states
77 FIELD Section Title:Magnetic Phenomena Laboratoire de Physico-Chimie des Solides Moleculaires Institut Lavoisier, UMR 8637,Universite de Versailles Saint-Quentin,Versailles,Fr. FIELD URL: written in English.Two new azido-bridged polyoxometalate compds. were synthesized in acetonitrile/methanol media and their mol. structures have been detd. by X-ray crystallog. The [{(g-SiW10O36)Mn2(OH)2(N3)0.5 (H2O)0.5}2(m-1,3-N3)]10-(1a) tetranuclear MnIII complex, in which an end-to-end N3- ligand acts as a linker between two [(g-SiW10O36)Mn2(OH)2]4- units, represents the first manganese-azido polyoxometalate. The magnetic properties have been studied considering the spin Hamiltonian H = -J1(S1S2+S1*S2*)-J2(S1S1*), showing that antiferromagnetic interactions between the paramagnetic centers (g = 1.98) occur both through the di-(m-OH) bridge (J1 = -25.5 cm-1) and the m-1,3-azido bridge (J2 = -19.6 cm-1). The [(g-SiW10O36)2Cu4(m-1,1,1-N3)2(m-1,1-N3)2]12- (2a) tetranuclear CuII complex consists of two [g-SiW10O36Cu2(N3)2]6- subunits connected through the two m-1,1,1-azido ligands, the four paramagnetic centers forming a lozenge. The magnetic susceptibility data have been fitted. This reveals ferromagnetic interactions between the four CuII centers, leading to an S = 2 ground state (H = -J1(S1S2+S1*S2*)-J2 (S2S2*), J1 = +294.5 cm-1, J2 = +1.6 cm-1, g = 2.085). The ferromagnetic coupling between the CuII centers in each subunit is the strongest ever obsd. either in a polyoxometalate compd. or in a diazido-bridged CuII complex. Considering complex 2a and the previously reported basal-basal di-(m-1,1-N3)-bridged CuII complexes in which the metallic centers are not connected by other magnetically coupling ligands, the linear correlation J1 = 2639.5-24.95*qav between the qav bridging angle and the J1 coupling parameter has been proposed. The electronic structure of complex 2a has also been investigated by using multifrequency high-field ESR (HFEPR) spectroscopy between 95 and 285 GHz. The spin Hamiltonian parameters of the S = 2 ground state (D = -0.135(2) cm-1, E = -0.003(2) cm-1, gx = 2.290(5), gy = 2.135(10), gz = 2.158(5)) as well as of the first excited spin state S = 1 (D = -0.960(4) cm-1, E = -0.080(5) cm-1, gx = 2.042(5), gy = 2.335(5), gz = 2.095(5)) have been detd., since the energy gap between these two spin states is very small (1.6 cm-1). [on SciFinder (R)
First Keto-Functionalized Microporous Al-Based Metal–Organic Framework: [Al(OH)(O<sub>2</sub>C‑C<sub>6</sub>H<sub>4</sub>‑CO‑C<sub>6</sub>H<sub>4</sub>‑CO<sub>2</sub>)]
Based on the V-shaped linker molecule 4,4′-benzophenonedicarboxylic
acid, the new carbonyl-functionalized metal–organic framework
(MOF) [Al(OH)(O<sub>2</sub>C-C<sub>6</sub>H<sub>4</sub>-CO-C<sub>6</sub>H<sub>4</sub>-CO<sub>2</sub>)], denoted as CAU-8, was discovered
employing high-throughput methods. The compound is obtained from 4,4′-benzophenonedicarboxylic
acid, Al<sub>2</sub>(SO<sub>4</sub>)<sub>3</sub>·18H<sub>2</sub>O in a mixture of <i>N</i>,<i>N</i>-dimethylformamide
(DMF) and water under solvothermal conditions. The structure was determined
from single-crystal X-ray diffraction data (<i>I</i>4<sub>1</sub>/<i>a</i>, <i>a</i> = <i>b</i> = 13.0625(5), <i>c</i> = 52.565(2) Å). The framework
is based on infinite inorganic building units of <i>trans</i>-connected, corner-sharing AlO<sub>6</sub>-polyhedra. Parallel Al–O-chains
are arranged in layers perpendicular to [001]. Within a layer an interchain
distance of ∼1.1 nm is observed. The orientation of the Al–O-chains
within neighboring layers is perpendicular to each other, along [100]
and [010], respectively, and an ABCDA stacking of these layers is
observed. The interconnection of these orthogonally oriented chains
by the V-shaped dicarboxylate ions results in the formation a three-dimensional
framework structure containing one-dimensional channels with a diameter
of about 8 Å. The pore walls are lined by the keto-groups. CAU-8
was thoroughly characterized by X-ray powder diffraction (XRPD), thermogravimetric
measurements, IR- and Raman-spectroscopy, elemental analysis, and
gas sorption experiments using N<sub>2</sub> and H<sub>2</sub> as
adsorptives. CAU-8 is stable up to 350 °C in air and exhibits
a moderate porosity with a specific surface area of <i>S</i><sub>BET</sub> = 600 m<sup>2</sup>/g and a micropore volume of 0.23
cm<sup>3</sup>/g. Moreover, a detailed topological analysis of the
framework was carried out, and an approach for the topological analysis
of MOFs based on infinite 1-periodic building units is proposed
HF-Induced Intramolecular C -Arylation and C -Alkylation/Fluorination of 2-Aminoglycopyranoses
International audienc
Combined XRD and infrared studies of pyridinium species in (PyH)(3)[PW12O40] single crystals
International audienceThe pyridinium salts of 12-tungstophosphoric acid (PyH)(3)[PW12O40]center dot 2CH(3)CN (1) and (PyH)(3)[PW12O40] (2) have been prepared and studied by single crystal and powder X-ray diffraction (XRD) in order to characterize the crystallographic sites occupied by the pyridinium species. The three PyH+ species are located on two unequivalent sites. Two species are linearly H-bonded to the oxygen atoms of the Keggins unit (alpha species), whereas the third one (beta) forms a bent H-bond. In order to determine the infrared bands characterizing each type of pyridinium species in the 1650-1300 cm(-1) range, infrared spectra have been recorded from room temperature to 100 K. They reveal that only a pyridinium species give rise to the unusual splitting of the PyH+ nu 8b and nu 19b modes, whereas beta pyridinium species lead to a classical pyridinium spectrum