Inside Cover: Hydrogen-Bonded Open-Framework with Pyridyl-Decorated Channels: Straightforward Preparation and Insight into Its Affinity for Acidic Molecules in Solution (Chem. Eur. J. 49/2017)

International audience; A hydrogen-bonded open framework with pores decorated by pyridyl groups was constructed by off-charge-stoichiometry assembly of protonated tetrakis(4-pyridyloxymethyl)methane and [Al(oxalate)(3)](3-), which are the H-bond donor and acceptor of ionic H-bond interactions, respectively. This supramolecular porous architecture (SPA-2) has 1nm-large pores interconnected in 3D with large solvent-accessible void (53%). It demonstrated remarkable affinity for acidic organic molecules in solution, which was investigated by means of various carboxylic acids including larger drug molecules. Competing sorption between acetic acid and its halogenated homologues evidenced good sel…

Efficiency of dihydroxamic and trihydroxamic siderochelates to extract uranium and plutonium from contaminated soils

International audience; Actinide-based mineral phases occurring in contaminated soils can be solubilized by organic chelators excreted by plants, such as citrate. Herein, the efficiency of citrate towards U and Pu extraction is compared to that of siderophores, whose primary function is the acquisition of iron(III) as an essential nutrient and growth factor for many soil microorganisms. To that end, we selected desferrioxamine B (DFB) as an emblematic bacterial trishydroxamic siderophore and a synthetic analog, abbreviated (LCy,Pr)H2, of the tetradentate rhodotorulic acid (RA) produced by yeasts. Firstly, the uranyl speciation with both ligands was assessed in the pH range 2–11 by potentiom…

Self-Assembly of Zr(C2O4)44– Metallotectons and Bisimidazolium Cations: Influence of the Dication on H-Bonded Framework Dimensionality and Material Potential Porosity

Assemblies involving [Zr(C2O4)4]4– metallotectons (C2O42– = oxalate) and linear, flexible, or V-shaped organic cations (H2-Lx)2+ derived from the 1,4-bisimidazol-1-ylbenzene molecule have been envisioned to elaborate porous frameworks based on ionic H-bonds. Five architectures of formula [{(H2-L1)2Zr(C2O4)4}·2H2O] (1), [{(H2-L2)2Zr(C2O4)4}·6H2O] (2), [{(H2-L3)2Zr(C2O4)4}·6H2O] (3), [{(H2-L4)2Zr(C2O4)4}·H2O] (4), and [{(H2-L5)2Zr(C2O4)4}·6H2O] (5) (with L1 = p-bis(imidazol-1-yl)benzene, L2 = p-bis(2-methylimidazol-1-yl)benzene, L3 = p-bis(imidazol-1-yl)-2,5-dimethylbenzene, L4 = p-bis(imidazol-1-ylmethyl)benzene, L5 = m-bis(imidazol-1-yl)benzene) have been obtained; 1–3, and 5 show an open-f…

Surface Acoustic Wave Sensors for the Detection of Hazardous Compounds in Indoor Air

Presented at the Eurosensors 2017 Conference, Paris, France, 3–6 September 2017.; International audience; In this work, the authors show the capabilities of Surface Acoustic Wave (SAW) devices coupled with various absorbents to probe the properties of gas sensitive materials for the manufacturing of hazardous gas sensors. The great capabilities of cobalt corroles for the trapping of carbon monoxide (CO) were exploited to produce selective sensors. These corroles were deposited on SAW delay lines surfaces and then exposed to carbon monoxide (CO) in standard conditions. Concentrations of a few hundreds of ppb were measured emphasizing the interest of such sensors for the detection of CO. Anot…

A Study Using X-ray Absorption and Emission Spectroscopy of Dioxygen-Binding Xerogels Incorporating Cyclam Units Complexed with Copper Salts.

X-ray absorption spectroscopy was used to elucidate how hybrid xerogels complexed with CuCl2 could reversibly bind molecular dioxygen. Difference EXAFS analyses at the Cu K-edge suggest that dioxygen could bridge two Cu atoms in a μ-η1:η1 peroxo-like conformation with unequal Cu···O distances. Only the short distance (RCu–O1 = 1.86 ± 0.01 A) was unambiguously determined and looks typical of a CuII site. The Cu···Cu internuclear distances would be rather long: RCu–Cu ≈ 4.0 A (3.9 A) for the oxygenated (oxygen-free) xerogels. Cl K-edge EXAFS spectra revealed the pre-existence in the oxygen-free xerogels of CuI sites with short Cl–Cu bonds (2.11 ± 0.03 A). Pentacoordinate CuII sites with a lon…

Synthesis of Macropolycyclic Ligands Based on Tetraazacycloalkanes

A versatile synthesis of spherical macrobicyclic and cylindrical macrotricyclic ligands is described using 1,4,8,11-tetraazacyclotetradecane (cyclam), 1,4,7,10-tetraazacyclododecane (cyclen), or dioxo macrocycles as precursors. Macrobicycles have been obtained by allowing cyclam, cyclen, or 5,12-dioxocyclam (1,4,8,11-tetraazacyclotetradecane-5,12-dione) to react with a bis-electrophilic spacer under high dilution conditions. A surprising selectivity has been observed for 2,6-dioxocyclen (1,4,7,10-tetraazacyclododecane-2,6-dione), which yields only macrotricycles under the same reaction conditions. Molecular modelling studies have been carried out to investigate the selectivity of the reacti…

Equilibrium and structural studies of complexes with a hexadentate ligand containing amide, amine and pyridyl nitrogen donors. Crystal structures of copper(II), nickel(II) and cobalt(III) complexes

A novel potentially hexadentate ligand, 1,8-bis(2-pyridylcarbamoyl)-3,6-diazaoctane (pyctrien) has been synthesised as its tetrahydrochloride salt; its protonation constants and the stability constants of the copper(II) and nickel(II) chelates have been determined by potentiometry. Amide group deprotonation permits the formation of [MLH−1]+ and [MLH−2] species in all cases, whereas the detection of the neutral or the protonated species depends on the nature of the metal ions. The solid complexes of copper, nickel and cobalt with the neutral and the deprotonated ligand have been synthesised and characterised by IR and UV–VIS spectroscopy. The amidic groups are coordinated through the oxygen …

Porous materials applied to biomarker sensing in exhaled breath for monitoring and detecting non-invasive pathologies

International audience; Overview of the use of porous materials for gas sensing to analyze the exhaled breath of patients for disease identification.The quantification of specific gases among thousand of VOCs (Volatile Organic Compounds) present in the human breath at the ppm/ppb level can be used to evidence the presence of diseases in the human body. The detection of these biomarkers in human exhaled breath through a noninvasive approach is an important field of research which is still attracting important attention to this day. A portable device working at room temperature and usable directly on exhaled breath samples is still a challenge requiring a sensing material with high performanc…

Cobalt Corroles with Bis‐Ammonia or Mono‐DMSO Axial Ligands. Electrochemical, Spectroscopic Characterizations and Ligand Binding Properties

International audience; Four bis-ammonia ligated cobalt corroles and four mono-DMSO ligated cobalt corroles with different mesoaryl substituents on the macrocycle (A 2 Band A 3-corroles) were synthesized and investigated as to their electrochemical and spec-troscopic properties under different solution conditions. The complexation energies of the investigated cobalt corroles were theoretically calculated to illustrate the propensity of the cobalt center for pentacoordination or hexa-coordination with various axial ligands (DMSO, CO, py and NH 3). The structure of one hexacoordinate bis-NH 3 cobalt corrole complex was also determined by X-ray diffraction.

Some factors affecting the removal of lead(II) ions from aqueous solution by porous hydroxyapatite: relationships between surface and adsorption properties

A porous hydroxyapatite (p-HAp) was prepared and employed for the removal of lead(II) ions at different concentrations from aqueous solution to determine the adsorption properties of p-HAp and compare them with those of a commercial hydroxyapatite (CAp) sample. The kinetic data obtained indicated that the adsorption performances of the adsorbents depended both on their specific surface area and crystallinity. Complexation of the Pb(II) ion on the adsorbent surface favoured the dissolution of hydroxyapatites characterized by a Ca/Pb molar ratio in the 0.85–1.5 range. The maximum adsorption capacity of p-Hap for Pb(II) ions at 30 ± 2°C was 2.30 mmol/g relative to 1.38 mmol/g for the commercia…

Copper(II) and nickel(II) complexes of pyridylamido hexadentate ligands: chemical speciation and spectroscopic studies

Abstract Two novel potentially hexadentate ligands, 1,10-(2-bis picolinamide)-4,7-diazadecane (pycdpnen) and 1,8-bis(2-picolinamide)-3,6-dioxaoctane (pycdado) have been synthesised as their hydrochloride salt; its protonation constants and the stability constants of the copper(II) and nickel(II) chelates have been determined by potentiometry. Amide groups deprotonation permits the formation of [MLH −1 ] + species in all cases, while only pycdado gives [MLH −2 ] species. The solid complexes of copper and nickel with the neutral and the deprotonated ligands have been synthesised and characterised by IR, UV–Vis and ESR spectroscopy. The amidic groups are coordinated through the oxygen atoms in…

Covalent Organic Frameworks for the detection of CO

International audience; Every year in the world, carbon monoxide (CO) is responsible for thousands of intoxications and hundreds of deaths. The detection (CO) at few ppm levels is thus a critical point for the control of the air quality. Corrole belongs to the family of porphyrinoids which is largely used for sensing applications [1]. We have shown that cobalt metallocorroles are able to bind carbon monoxide in the axial position with a high affinity even in the presence of nitrogen and dioxygen, the two main components of the atmosphere [2]. We have recently prepared sensing devices for low CO detection level (sub-ppm) using cobalt corroles deposited as films on a Surface Acoustic Wave dev…

Diamondoid Nanostructures as sp 3 ‐Carbon‐Based Gas Sensors

Diamondoids, sp3 -hybridized nanometer-sized diamond-like hydrocarbons (nanodiamonds), difunctionalized with hydroxy and primary phosphine oxide groups, enable the assembly of the first sp3 -C-based chemical sensors by vapor deposition. Both pristine nanodiamonds and palladium nanolayered composites can be used to detect toxic NO2 and NH3 gases. This carbon-based gas sensor technology allows reversible NO2 detection down to 50 ppb and NH3 detection at 25-100 ppm concentration with fast response and recovery processes at 100 °C. Reversible gas adsorption and detection is compatible with 50 % humidity conditions. Semiconducting p-type sensing properties are achieved from devices based on prim…

Coordination Chemistry in the Solid: Study of the Incorporation of CuII into Cyclam-Containing Hybrid Materials

Synthesis and Characterization of Copper Complexes Containing the Tripodal N7 Ligand Tris{2-[(pyridin-2-ylmethyl)amino]ethyl}amine (=N′-(Pyridin-2-ylmethyl)-N,N-bis{2-[(pyridin-2-ylmethyl)amino]ethyl}ethane-1,2-diamine): Equilibrium, Spectroscopic Data, and Crystal Structures of Mono- and Trinuclear Copper(II) Complexes

The stability constants of the CuII chelates with the tripodal heptadentate ligand tris{2-[(2-pyridylmethyl)amino]ethyl}amine (=N′-(pyridin-2-ylmethyl)-N,N-bis{2-[(pyridin-2-ylmethyl)amino]ethyl}ethane-1,2-diamine; tpaa), determined by potentiometry and UV spectrometry, show the formation of [Cu(tpaaH)]3+ and [Cu(tpaa)]2+ species. In the solid state, two mononuclear CuII compounds, [Cu(tpaa)](PF6)2 (1) and [Cu(tpaaH)](ClO4)3⋅H2O (2), and one trinuclear [Cu3(tpaa)2(ClO4)2](ClO4)4⋅2 H2O (3) complex were isolated and characterized by IR, UV/VIS, and EPR spectroscopy. An X-ray structure of the mononuclear protonated complex 2 shows that the Cu2+ ion has a distorted square-pyramidal geometry (τ=…

Exceptional affinity of nanostructured organic-inorganic hybrid materials towards dioxygen: confinement effect of copper complexes

We report the exceptional reactivity towards dioxygen of a nanostructured organic-inorganic hybrid material due to the confinement of copper cyclam within a silica matrix. The key step is the metalation reaction of the ligand, which can occur before or after xerogel formation through the sol-gel process. The incorporation of a Cu(II) center into the material after xerogel formation leads to a bridged Cu(I)/Cu(II) mixed-valence dinuclear species. This complex exhibits a very high affinity towards dioxygen, attributable to auto-organization of the active species in the solid. The remarkable properties of these copper complexes in the silica matrix demonstrate a high cooperative effect for O(2…

Ordered mesoporous hybrid materials containing cobalt(ii) Schiff base complex

Immobilisation of Co-salen and Co-fluomine onto ordered mesoporous silica has been achieved through coordination of the cobalt to pyridine or imidazole groups covalently attached to the silica matrix. Two routes have been investigated to obtain mesoporous hybrid materials containing coordinating ligands: post synthesis grafting of 4-[2-(trimethoxysilyl)ethyl]pyridine 1 and N-trimethoxysilylpropylimidazole 2 on hexagonally ordered mesoporous silica via SiOH groups or direct synthesis method i.e. co-hydrolysis and polycondensation of the same functionalised organotrimethoxysilane with a number of equivalents of TEOS in the presence of n-hexadecylamine as structure directing agent. The first m…

Effects of preorganization in the chelation of UO22+ by hydroxamate ligands: cyclic PIPO– vs linear NMA–

International audience; Many siderophores incorporate as bidentate chelating subunits linear and more seldomly cyclic hydroxamate groups. In this work, a comparative study of the uranyl binding properties in aqueous solution of two monohydroxamic acids, the prototypical linear N-methylacetohydroxamic acid (NMAH) and the cyclic analog 1-hydroxypiperidine-2-one (PIPOH), has been carried out. The complex [UO2(PIPO)(2)(H2O)] crystallized from slightly acidic water solutions (pH < 5), and its molecular structure was determined by X-ray diffraction. The uranyl speciation in the presence of both ligands has been thoroughly investigated in a 0.1 M KNO3 medium at 298.2 K by the combined use of four …

Organic-Inorganic Hybrid Sol-Gel Materials Incorporating Functionalized Cobalt(III) Corroles for the Selective Detection of CO

Selective CO2 adsorption by a triazacyclononane-bridged microporous metal-organic framework.

Metal-organic frameworks constructed by self-assembly of metal ions and organic linkers have recently been of great interest in the preparation of porous hybrid materials with a wide variety of functions. Despite much research in this area and the large choice of building blocks used to fine-tune pore size and structure, it remains a challenge to synthesise frameworks composed of polyamines to tailor the porosity and adsorption properties for CO(2). Herein, we describe a rigid and microporous three-dimensional metal-organic framework with the formula [Zn(2)(L)(H(2)O)]Cl (L=1,4,7-tris(4-carboxybenzyl)-1,4,7-triazacyclononane) synthesised in a one-pot solvothermal reaction between zinc ions a…

Planar-Chiral 1,1 '-Diboryl Metallocenes: Diastereoselective Synthesis from Boryl Cyclopentadienides and Spin Density Analysis of a Diborylcobaltocene

International audience; The reaction of nonsubstituted alkali metal cyclopentadienides with haloboranes leads to similar to 90:10 mixtures of isomeric diene products that can be deprotonated to give simple boryl cyclopentadienides. We extended this transformation to the sterically hindered lithium tert-butylcyclopentadienide 1 using FBMe(s)2 (Mes = 2,4,6-trimethylphenyl) and ClBCy2 as electrophiles. The boryl group is selectively introduced in the remote position to minimize steric congestion. The new boryl dienes are obtained as mixtures of isomers, and subsequent deprotonation with MeLi or LiHMDS affords the lithium 1,3-disubstituted cyclopentadienides Sa,b in yields over 95%. Direct asse…

Efficient growth of sub-micrometric MOF crystals inside the channels of AAO membranes

International audience; A dynamic step-by-step methodology has been implemented to grow the HKUST-1 porous coordination polymer inside commercial anodic aluminium oxide membranes. Efficient crystal growth is achieved from the membrane inner walls and over the whole membrane thickness when copper acetate colloidal suspensions and benzene tricarboxylic acid solutions are forced to flow through the membrane. Sorption properties of the HKUST-1 embedded in membranes show selectivity for CO2 over CO, CH4, O2 and N2 similar to the bulk material.

A two-step synthesis of new macrobicyclic aza-ligands starting from “trans”dioxocyclam as diprotected macrocycle

Abstract A rapid and convenient synthesis of two small aza-cryptands containing a 1,4,8,11-tetraazacyclotetradecane backbone is reported. This strategy can be applied to the preparation of many other aza-cages by varying the nature of the cross linker. Moreover, the two remaining secondary amine sites may allow the functionalization of these ligands or their grafting on a polymer.

Immobilization of copper complexes with (1,10-phenanthrolinyl)phosphonates on titania supports for sustainable catalysis

Different strategies for the immobilization of copper complexes with 1,10-phenanthroline (phen) using the phosphonate anchoring group were investigated to prepare robust and porous heterogeneous catalysts. Homoleptic and heteroleptic copper(I) complexes with phen bearing the bis(trimethylsiloxy)phosphoryl anchoring group (Pphen-Si) at different positions of the phen backbone were prepared and covalently incorporated into titania (TiO2) xerogels by using the sol–gel process or grafted onto the surface of mesoporous TiO2 (SBET = 650 m2 g−1). Copper(I) bis(Pphen-Si) complexes were the only complexes that were successfully anchored onto the TiO2 surface because the heterogenization was often ac…

Water sorption isotherms of molecularly imprinted polymers. Relation between water binding and iprodione binding capacity

International audience; Molecularly imprinted polymers are often used in aqueous medium in order to recognize specifically a target molecule. The molecular recognition is usually based on hydrogen bonding. In this case, water molecule presents a serious competition towards the target molecule. In this study, the water sorption by molecularly imprinted polymers was studied in aqueous medium. The molecularly imprinted polymers were specific for iprodione fungicide and were prepared using a 24 full factorial experimental design. They were synthesized using EGDMA or TRIM as crosslinker, methacrylamide or styrene as functional monomer and using bulk or precipitation polymerization. The water sor…

Hydrogen-Bonded Open-Framework with Pyridyl-Decorated Channels: Straightforward Preparation and Insight into Its Affinity for Acidic Molecules in Solution.

International audience; An hydrogen-bonded open framework with pores decorated by pyridyl groups has been constructed following an off-charge-stoichiometry assemblage of protonated tetrakis(4-pyridyl-oxymethyl)methane and [Al(oxalate)3]3-, respectively the H-bond donor and acceptor of the ionic H-bond interactions. This supramolecular porous architecture (SPA-2) possesses 1 nm-large pores interconnected in 3D with high solvent accessible void (53%). It demonstrated remarkable affinity for acidic organic molecules in solution, which was investigated by the means of various carboxylic acids including larger drug molecules. Noteworthy, competing sorption between acetic acid and its halogenated…

Coordinatively Unsaturated Amidotitanocene Cations with Inverted σ and π Bond Strengths: Controlled Release of Aminyl Radicals and Hydrogenation/Dehydrogenation Catalysis

Cationic amidotitanocene complexes [Cp2 Ti(NPhAr)][B(C6 F5 )4 ] (Cp=η5 -C5 H5 ; Ar=phenyl (1 a), p-tolyl (1 b), p-anisyl (1 c)) were isolated. The bonding situation was studied by DFT (Density Functional Theory) using EDA-NOCV (Energy Decomposition Analysis with Natural Orbitals for Chemical Valence). The polar Ti-N bond in 1 a-c features an unusual inversion of σ and π bond strengths responsible for the balance between stability and reactivity in these coordinatively unsaturated species. In solution, 1 a-c undergo photolytic Ti-N cleavage to release Ti(III) species and aminyl radicals ⋅NPhAr. Reaction of 1 b with H3 BNHMe2 results in fast homolytic Ti-N cleavage to give [Cp2 Ti(H3 BNHMe2 )…

Tetradihydrobenzoquinonate and Tetrachloranilate Zr(IV) Complexes: Single-Crystal-to-Single-Crystal Phase Transition and Open-Framework Behavior for K4Zr(DBQ)4.

The molecular complexes K4[Zr(DBQ)4] and K 4[Zr(CA)4], where DBQ2- and CA2- stand respectively for deprotonated dihydroxybenzoquinone and chloranilic acid, are reported. The anionic metal complexes consist of Zr(IV) surrounded by four O,O-chelating ligands. Besides the preparation and crystal structures for the two complexes, we show that in the solid state the DBQ complex forms a 3-D open framework (with 22% accessible volume) that undergoes a crystal-to-crystal phase transition to a compact structure upon guest molecule release. This process is reversible. In the presence of H2O, CO2, and other small molecules, the framework opens and accommodates guest molecules. CO2 adsorption isotherms…

Electrochemistry of Bis(pyridine)cobalt (Nitrophenyl)corroles in Nonaqueous Media

International audience; A series of bis(pyridine)cobalt corroles with one or three nitrophenyl groups on the meso positions of the corrole macrocycle were synthesized and characterized as to their electrochemical and spectroscopic properties in dichloromethane, benzonitrile, and pyridine. The potentials for each electrode reaction were measured by cyclic voltammetry and the electron-transfer mechanisms evaluated by analysis of the electrochemical data combined with UV-visible spectra of the neutral, electroreduced, and electroxidized forms of the corroles. The proposed electronic configurations of the initial compounds and the prevailing redox reactions involving the electroactive central c…

Conformational and structural studies of N-methylacetohydroxamic acid and of its mono- and bis-chelated uranium(VI) complexes

The thermodynamics and kinetics of the cis/trans isomerism of N-methylacetohydroxamic acid (NMAH) and its conjugated base (NMA(-)) have been reinvestigated in aqueous media by (1)H NMR spectroscopy. Hindered rotation around the central C-N bond due to electronic delocalization becomes slow enough on the NMR time scale to observe both rotamers in equilibrium in D2O at room temperature. By properly assigning the methyl group resonances, evidence for the prevalence of the E over the Z form is unambiguously provided [K300=[E]/[Z]=2.86(2) and 9.63(5) for NMAH and NMA(-), respectively], closing thereby a long-lasting dispute about the most stable conformer. To that end, calculations of the chemic…

SAW based CO2 sensor: influence of functionalizing MOF crystal size on the sensor's selectivity

International audience; The potential impact of indoor air quality on human health has become an increasingly important topic of public health and, thus, has stimulated an interest in hazardous compounds survey such as carbon dioxide. To address this issue, we started the development of a Surface Acoustic Wave device functionalized with metal-organic framework for the selective detection of carbon dioxide. Here, we propose preliminary results on the influence of the size of the metal-organic framework crystals on the sensor’s selectivity and on its evolution with the ageing of the sensor

Electrochemistry of Mono- and Bis-CN Ligated Cobalt Corroles

International audience; The electrochemical properties of numerous transition metal corroles have been examined under a variety of<br&gtsolution condition with special emphasis being placed on the innocent or non-innocent nature of the corrole<br&gtmacrocycle. This property, as well as the half-wave potentials and sites of electron transfers, are known to be<br&gtstrongly influenced by the type of central metal ion and degree of axial coordination, namely 4, 5 or 6-coordinate.<br&gtThe redox potentials of metallocorroles are also dependent upon the solvent and inductive, resonance or steric<br&gteffects dictated by peripheral substituents at the meso or β-pyrrole positions of the corrole li…

Insights into the crystal packing of phosphorylporphyrins based on the topology of their intermolecular interaction energies

Four metal complexes of 5,15-bis(diethoxyphosphoryl)-10,20-diphenylporphyrin 1M (M = Cd(II), Ni(II), Pd(II), and Pt(II)) were synthesized and crystallographically characterized. The crystal organization patterns were analyzed using DFT (B97-D3/def2-SVP) calculations of the intermolecular interaction energies between complexes in the crystals. For the systematic analysis of crystal packing, the calculations were extended to previously reported compounds 1M (M = H2, Cu(II), and Zn(II)). Quantitative analysis of the interaction energies shows the essential role of weak intermolecular interactions, such as C-H⋯O, C-H⋯π and M⋯π, in the formation of basic structural motifs and their organization …

Synthesis and Physicochemical Characterization ofmeso-Functionalized Corroles: Precursors of Organic-Inorganic Hybrid Materials

Cobalt(III) corroles exhibit an infinite selectivity for the coordination of carbon monoxide towards dioxygen and dinitrogen. This peculiar property thus allows their use as sensing devices for CO detection. Here are described the syntheses and physico-chemical characterization of meso mono-, bis- and tris(triethoxysilyl)-functionalized corroles, precursors of organic–inorganic materials. The corrole ring formation was achieved in every case using the “2+1” method involving the reaction of two equivalents of an encumbered dipyrromethane with one equivalent of an aromatic aldehyde in the presence of a catalytic amount of trifluoroacetic acid. The functionalization of the corrole by triethoxy…

Functionnalized Surface Acoustic Wave Sensors for the Detection of Hazardous Gases

International audience; In this work, we show the capabilities of Surface Acoustic Wave (SAW) devices to probe the properties of gas sensitive materials for the manufacturing of hazardous gas sensors. The great capabilities of cobalt corroles for the trapping of carbon monoxide (CO) were exploited to produce selective sensors. These corroles were deposited on SAW delay lines surfaces and then exposed to carbon monoxide (CO) in standard conditions. Concentrations of a few hundreds of ppb were measured emphasizing the interest of such sensors for the detection of CO. Another type of sensitive layers exhibiting specific porosity adapted to the trapping of formaldehyde (CH$_2$O) were deposited …

Exploiting Palladium-Catalyzed Cross-Coupling for the Synthesis of 2-Aryl-Substituted 1-Aminocyclopropylphosphonates

A series of 2-aryl-substituted 1-aminocyclopropylphosphonates containing an additional remote phosphonate group have been synthesized starting from readily accessible dimethyl (1 R *,2 R *)-2-(4-bromophenyl)-1-formamidocyclopropylphosphonate using cross-coupling methodology. Different types of palladium-catalyzed reactions for carbon–carbon and carbon–phosphorus bond formation were realized. In each case the optimum conditions were found to obtain the desired products in high yield in both small- and large-scale experiments.

Mono-DMSO ligated cobalt nitrophenylcorroles: electrochemical and spectral characterization

Four mono-DMSO ligated cobalt corroles with one or three meso-nitrophenyl substituents on the macrocycle were synthesized and investigated as to their electrochemical and spectroscopic properties in CH2Cl2 and DMSO. Comparisons are made between redox reactions of the five-coordinate DMSO adducts in the current study and earlier examined five- and six-coordinate cobalt corroles with pyridine axial ligands which were characterized in a variety of nonaqueous electrochemical solvents. The binding of carbon monoxide (CO) is also investigated.

Synthesis of large-pore ordered mesoporous silicas containing aminopropyl groups

Ordered mesoporous silicas with large-pore diameters incorporating aminopropyl groups in variable quantity have been synthesized via the co-condensation of tetraethyl orthosilicate (TEOS) and 3-tert-butyloxycarbonylaminopropyltriethoxysilane templated with nonionic surfactant P123 under acidic conditions. The deprotection of amino groups was then quantitatively achieved either by thermal treatment or acid hydrolysis followed by Et3N treatment, both routes leading to exactly the same materials. We showed that the free amino centers are fully accessible, by using the condensation of the amine function with benzaldehyde.

Room temperature ionic liquids based on cationic porphyrin derivatives and tetrakis(pentafluorophenyl)borate anion

A series of 11 low melting ionic liquids based on meso-substituted A3B -porphyrins and A2B2-porphyrins containing one or two pyridyl substituents have been synthesized in high yields. Three of them are liquids at room temperature. All these porphyrinic salts were characterized by1H NMR,19F NMR, MALDI-TOF mass spectrometry, elemental analysis and UV-visible spectroscopy. The thermal properties and conductivity values of these salt derivatives have been also measured. A specific conductivity value of up to 4 mS.cm-1could be obtained for a compound having the counter-anion B(C6F5)4-.

Factors affecting copper(II) binding to multiarmed cyclam-grafted mesoporous silica in aqueous solution

Single- as well as multi-anchored cyclam-functionalized silica samples have been prepared by grafting amorphous silica gel (K60) and mesostructured silica (SBA-15) with silylated cyclam precursors bearing one, two, or four triethoxysilyl groups, respectively ascribed to cyclam-mono, cyclam-di, and cyclam-tetra. Their reactivity toward copper(II) has been thoroughly investigated in aqueous solution and discussed with respect to the number of arms tethering the ligand to the silica surface and the structural ordering of the adsorbent in terms of capacity, long-term stability, and speed of access to the binding sites. Less-than-complete metal ion uptake was always observed, even in excess of c…

Porous Organic Polymers (POPs) based on cobalt corroles for the detection of carbon monoxide

International audience; Detection of carbon monoxide (CO) at few ppm levels is a critical point for quality control of domestic and<br&gtindustrial environment. CO is responsible for thousands of intoxications and hundreds of deaths per year in the<br&gtworld. Moreover, CO is a residual gas found in the industrial dihydrogen used for Proton Exchange Membrane<br&gtfuel cell, and deactivates the fuel cell prematurely. Corroles have been largely used in sensing applications.[1]<br&gtCobalt corroles display high binding affinity for carbon monoxide even in the presence of nitrogen and<br&gtdioxygen.[2] The affinity of the Co(III) metallocorroles for CO is directly correlated with the Lewis acid…

Ligand Noninnocence in Cobalt Dipyrrin–Bisphenols: Spectroscopic, Electrochemical, and Theoretical Insights Indicating an Emerging Analogy with Corroles

Three cobalt dipyrrin-bisphenol (DPPCo) complexes with different meso-aryl groups (pentafluorophenyl, phenyl, and mesityl) were synthesized and characterized based on their electrochemistry and spectroscopic properties in nonaqueous media. Each DPPCo undergoes multiple oxidations and reductions with the potentials, reversibility, and number of processes depending on the specific solution conditions, the specific macrocyclic substituents, and the type and number of axially coordinated ligands on the central cobalt ion. Theoretical calculations of the compounds with different coordination numbers are given in the current study in order to elucidate the cobalt-ion oxidation state and the innoc…

Nanocatalysts for High Selectivity Enyne Cyclization: Oxidative Surface Reorganization of Gold Sub-2-nm Nanoparticle Networks

International audience; Ultrasmall gold nanoparticles (NPs) stabilized in networks by polymantane ligands (diamondoids) were successfully used as precatalysts for highly selective heterogeneous gold-catalyzed dimethyl allyl(propargyl)malonate cyclization to 5-membered conjugated diene. Such reaction usually suffers from selectivity issues with homogeneous catalysts. This control over selectivity further opened the way to one-pot cascade reaction, as illustrated by the 1,6-enyne cycloisomerization–Diels–Alder reaction of dimethyl allyl propargyl malonate with maleic anhydride. The ability to assemble nanoparticles with controllable sizes and shapes within networks concerns research in sensor…

The Taming of Redox‐Labile Phosphidotitanocene Cations

International audience; Tame d0 phosphidotitanocene cations stabilized with a pendant tertiary phosphane arm are reported. These compounds were obtained by one-electron oxidation of d1 precursors with [Cp2Fe][BPh4]. The electronic structure of these compounds was studied experimentally (EPR, UV/Vis, and NMR spectroscopy, X-ray diffraction analysis) and through DFT calculations. The theoretical analysis of the bonding situation by using the electron localization function (ELF) shows the presence of π-interactions between the phosphido ligand and Ti in the d0 complexes, whereas dπ–pπ repulsion prevents such interactions in the d1 complexes. In addition, CH–π interactions were observed in seve…

Influence of interfering gases on a carbon monoxide differential sensor based on SAW devices functionalized with cobalt and copper corroles

International audience; <!--[if gte mso 9]&gt<xml&gt <w:WordDocument&gt <w:View&gtNormal</w:View&gt <w:Zoom&gt0</w:Zoom&gt <w:TrackMoves/&gt <w:TrackFormatting/&gt <w:HyphenationZone&gt21</w:HyphenationZone&gt <w:PunctuationKerning/&gt <w:ValidateAgainstSchemas/&gt <w:SaveIfXMLInvalid&gtfalse</w:SaveIfXMLInvalid&gt <w:IgnoreMixedContent&gtfalse</w:IgnoreMixedContent&gt <w:AlwaysShowPlaceholderText&gtfalse</w:AlwaysShowPlaceholderText&gt <w:DoNotPromoteQF/&gt <w:LidThemeOther&gtFR</w:LidThemeOther&gt <w:Compatibility&gt <w:BreakWrappedTables/&gt <w:SnapToGridInCell/&gt <w:WrapTextWithPunct/&gt <w:UseAsianBreakRules/&gt <w:DontGrowAutofit/&gt <w:SplitPgBreakAndParaMark/&gt <w:EnableOpenTypeKe…

From ZIF-8@Al2O3Composites to Self-Supported ZIF-8 One-Dimensional Superstructures

International audience; Efficient preparation of composite materials consisting of ZIF-8 nanocrystals embedded inside the channels of macroporous anodic aluminum oxide membranes is reported. 1-D self-supported ZIF-8 superstructures are recovered through matrix dissolution.

Copper( ii ) complexes with phosphorylated 1,10-phenanthrolines: from molecules to infinite supramolecular arrays

International audience; The reaction of phosphorylated 1,10-phenanthrolines 3-Pphen, 3,8-Pphen and 4,7-Pphen (3-Pphen = 3-diethoxyphosphorylphenanthroline, 3,8-Pphen = 3,8-bis(diethoxyphosphoryl) phenanthroline, 4,7-Pphen = 4,7-bis(diethoxyphosphoryl) phenanthroline) and hydrated copper(II) nitrate in a 1 : 1 ratio leads to the formation of supramolecular architectures. In the 1D coordination polymer [Cu(3-Pphen)(NO3)(2)](n) (2) the copper atom is coordinated to only one phenanthroline ligand and the coordination sphere is completed by two oxygen atoms of nitrate anions and the oxygen atom of the phosphoryl group from the neighbouring phenanthroline ligand. Complex Cu(3,8-Pphen)(NO3)(2) (3)…

Synthesis, characterization and X-ray crystal structures of cyclam derivatives. 7. Hydrogen-bond induced allosteric effects and protonation cooperativity in a macrotricyclic bisdioxocyclam receptor

The unprecedented cooperative protonation properties displayed by a barrel-shaped macrotricyclic tetraamine incorporating two 14-membered bisamide rings maintained in a face-to-face arrangement is rationalized in terms of allosteric effects upon binding of the first and third protons.

A robust nanoporous supramolecular metal–organic framework based on ionic hydrogen bonds

International audience; Hydrogen-bond assembly of tripod-like organic cations [H3-MeTrip]3+ (1,2,3-tri(4′-pyridinium-oxyl)-2-methylpropane) and the hexa-anionic complex [Zr2(oxalate)7]6− leads to a structurally, thermally, and chemically robust porous 3D supramolecular framework showing channels of 1 nm in width. Permanent porosity has been ascertained by analyzing the material at the single-crystal level during a sorption cycle. The framework crystal structure was found to remain the same for the native compound, its activated phase, and after guest resorption. The channels exhibit affinities for polar organic molecules ranging from simple alcohols to aniline. Halogenated molecules and I2 …

Selective chemisorption of carbon monoxide by organic-inorganic hybrid materials incorporating cobalt(III) corroles as sensing components.

Twenty-one hybrid materials incorporating cobalt(III) corrole complexes were synthesized by a sol–gel process or by grafting the metallocorrole onto a mesostructured silica of the SBA-15 type. All the materials show an almost infinite selectivity for carbon monoxide with respect to dinitrogen and dioxygen in the low-pressure domain where the chemisorption phenomenon is predominant. This peculiar property is of prime importance for an application as a CO sensor. The selectivity slightly decreases at high pressures where nonselective physisorption phenomena mainly occur. The percentage of active sites for CO chemisorption ranges from 22 to 64 %. This low percentage may be attributable to inte…

Structural and Electrochemical Studies of Copper(I) Complexes with Diethoxyphosphoryl-1,10-phenanthrolines

Two series of copper(I) complexes with diethoxyphosphoryl-substituted 1,10-phenanthroline ligands were synthesized and characterized in the solid state and in solution. The first comprised mixed-ligand CuI complexes with phenanthroline and triphenylphosphine. The second series includes bis-chelates with two phenanthroline ligands. According to the X-ray data for the six complexes, the ditopic phenanthroline ligands exhibit bidentate coordination to the copper(I) atom through two nitrogen atoms in both series. Solution equilibria involving different phenanthroline copper(I) species were studied by 1H and 31P NMR spectroscopy, electrochemistry, and spectroelectrochemistry. The solution specia…

Cadmium Metal–Organic Frameworks Based on Ditopic Triazamacrocyclic Linkers: Unusual Structural Features and Selective CO 2 Capture

International audience; Two three-dimensional cadmium metal organic frameworks with general formula [Cd-2(L-1)(H2O)(3)](NO3)(0.7)(HCOO)(0.2)Br-0.1 (Cd2L1, L-1 = 1,4,7-tris(4-carboxybenzy1)-1,4,7-triazacyclononane) and Cd(HL2)(H2O)(2) (CdL2, L-2 = 1,4,7-tris(3-(4-benzoate)prop-2-yn-1-yl)-1,4,7-triazacydononane) based on 1,4,7-triazacyclononane N-functionalized by different arylcarboxylic acids were prepared under solvothermal conditions and characterized by single crystal X-ray analysis and porosity measurements. The crystal structure of Cd2L1 reveals a cationic net with a bcs topology,. and nodes are constituted by dinuclear cadmium complexes, in which each cadmium atom adopts a hexacoordin…

First copper(I) ferrocenyltetraphosphine complexes: possible involvement in Sonogashira cross-coupling reaction ?

Preparation and characterization of the first examples of copper(I) ferrocenylpolyphosphine complexes are reported. The molecular structure of complex {P,P′,P′′-[1,1′,2,2′-tetrakis(diphenylphosphino)-4,4′-di-tert-butylferrocene]iodocopper(I)} (1) was solved by X-ray diffraction studies, and its fluxional behavior in solution was investigated by VT-31P NMR; both revealed a net triligated coordination preference of the ferrocenyl tetraphosphine Fc(P)4tBu with copper. The tetradentate ligand is an active auxiliary in Sonogashira alkynylation; therefore the general question of copper as a competitive coordination partner in the Pd/Cu-catalyzed Sonogashira reaction was raised and discussed. Elec…

Reversible coordination of dioxygen by tripodal tetraamine copper complexes incorporated in a porous silica framework.

The present study reports the synthesis and rational design of porous structured materials by using a templating method. A tetraethoxysilylated tripodal tetraamine (TREN) was covalently incorporated in a silica framework with a double imprint: A surfactant template and a metal ion imprint. The presence of a cationic surfactant (CTAB) endowed the material with a high porosity, and the tripodal or square-pyramidal topology of the ligand was preserved thanks to the use of the silylated Cu(II) complex. After removal of the surfactant and de-metalation, the incorporated tetraamine was quantitatively complexed by CuCl(2) and the material has shown after thermal activation that a reversible bindin…

Supramolecular open-framework architectures based on dicarboxylate H-bond acceptors and polytopic cations with three/four N–H+donor units

International audience; Supramolecular assemblages based on anionic H-acceptors and cationic H-donors have been envisioned to elaborate open frameworks maintained by ionic H-bonds. Combinations of di-anionic chloranilate (CA2-), oxalate (Ox2-), or terephthalate (BDC2-) and trisimidazolium or tetrapyridinium derivatives (three and four N-H+ donors, respectively) yielded five architectures of formulae [(H3TrIB)(CA)1.5[middle dot]2DMF[middle dot]2.5H2O] (1), [(H4Tetrapy)(CA)2[middle dot]3DMF] (2), [(H3TrIB)(HOx)(Ox)[middle dot]5H2O] (3), [(H4Tetrapy)(Ox)2[middle dot]5H2O] (4), and [(H4Tetrapy)(BDC)2(H2O)[middle dot]1DMF[middle dot]3H2O] (5) (with TrIB = 1,3,5-trisimidazolylbenzene and Tetrapy …

Reappraising Schmidpeter's bis(iminophosphoranyl)phosphides: coordination to transition metals and bonding analysis

The synthesis and characterization of a range of bis(iminophosphoranyl)phosphide (BIPP) group 4 and coinage metals complexes is reported. BIPP ligands bind group 4 metals in a pseudo fac-fashion, and the central phosphorus atom enables the formation of d0–d10 heterobimetallic complexes. Various DFT computational tools (including AIM, ELF and NCI) show that the phosphorus–metal interaction is either electrostatic (Ti) or dative (Au, Cu). A bridged homobimetallic Cu–Cu complex was also prepared and its spectroscopic properties were investigated. The theoretical analysis of the P–P bond in BIPP complexes reveals that (i) BIPP are closely related to ambiphilic triphosphenium (TP) cations; (ii) …

CCDC 960835: Experimental Crystal Structure Determination

Related Article: Alexander Yu. Mitrofanov, Yoann Rousselin, Roger Guilard, Stéphane Brandès, Alla G. Bessmertnykh-Lemeune, Marina A. Uvarova, Sergey E. Nefedov|2016|New J.Chem.|40|5896|doi:10.1039/C5NJ03572D

CCDC 1871410: Experimental Crystal Structure Determination

Related Article: Adrien T. Normand, Quentin Bonnin, Stéphane Brandès, Philippe Richard, Paul Fleurat-Lessard, Charles H. Devillers, Cédric Balan, Pierre Le Gendre, Gerald Kehr, Gerhard Erker|2019|Chem.-Eur.J.|25|2803|doi:10.1002/chem.201805430

CCDC 1042533: Experimental Crystal Structure Determination

Related Article: Stéphane Brandès, Alejandra Sornosa-Ten, Yoann Rousselin, Mickael Lagrelette, Christine Stern, Aurélien Moncomble, Jean-Paul Cornard, Michel Meyer|2015|J.Inorg.Biochem.|151|164|doi:10.1016/j.jinorgbio.2015.06.002

CCDC 1871415: Experimental Crystal Structure Determination

Related Article: Adrien T. Normand, Quentin Bonnin, Stéphane Brandès, Philippe Richard, Paul Fleurat-Lessard, Charles H. Devillers, Cédric Balan, Pierre Le Gendre, Gerald Kehr, Gerhard Erker|2019|Chem.-Eur.J.|25|2803|doi:10.1002/chem.201805430

CCDC 1871416: Experimental Crystal Structure Determination

Related Article: Adrien T. Normand, Quentin Bonnin, Stéphane Brandès, Philippe Richard, Paul Fleurat-Lessard, Charles H. Devillers, Cédric Balan, Pierre Le Gendre, Gerald Kehr, Gerhard Erker|2019|Chem.-Eur.J.|25|2803|doi:10.1002/chem.201805430

CCDC 1402188: Experimental Crystal Structure Determination

Related Article: Georges Mouchaham, Marion Gualino, Nans Roques, Carine Duhayon, Stéphane Brandès, Jean-Pascal Sutter|2015|CrystEngComm|17|8906|doi:10.1039/C5CE01070E

CCDC 1049575: Experimental Crystal Structure Determination

Related Article: Alexander Yu. Mitrofanov, Yoann Rousselin, Roger Guilard, Stéphane Brandès, Alla G. Bessmertnykh-Lemeune, Marina A. Uvarova, Sergey E. Nefedov|2016|New J.Chem.|40|5896|doi:10.1039/C5NJ03572D

CCDC 1871408: Experimental Crystal Structure Determination

Related Article: Adrien T. Normand, Quentin Bonnin, Stéphane Brandès, Philippe Richard, Paul Fleurat-Lessard, Charles H. Devillers, Cédric Balan, Pierre Le Gendre, Gerald Kehr, Gerhard Erker|2019|Chem.-Eur.J.|25|2803|doi:10.1002/chem.201805430

CCDC 1578032: Experimental Crystal Structure Determination

Related Article: Xiaoqin Jiang, Mario L. Naitana, Nicolas Desbois, Valentin Quesneau, Stéphane Brandès, Yoann Rousselin, Wenqian Shan, W. Ryan Osterloh, Virginie Blondeau-Patissier, Claude P. Gros, Karl M. Kadish|2018|Inorg.Chem.|57|1226|doi:10.1021/acs.inorgchem.7b02655

CCDC 1529941: Experimental Crystal Structure Determination

Related Article: Hervé Feuchter, Guillaume Ortiz, Yoann Rousselin, Alla Bessmertnykh-Lemeune, and Stéphane Brandès|2017|Cryst.Growth Des.|17|3665|doi:10.1021/acs.cgd.7b00217

CCDC 1529942: Experimental Crystal Structure Determination

Related Article: Hervé Feuchter, Guillaume Ortiz, Yoann Rousselin, Alla Bessmertnykh-Lemeune, and Stéphane Brandès|2017|Cryst.Growth Des.|17|3665|doi:10.1021/acs.cgd.7b00217

CCDC 1537659: Experimental Crystal Structure Determination

Related Article: Georges Mouchaham, Nans Roques, Walid Khodja, Carine Duhayon, Yannick Coppel, Stéphane Brandès, Tamás Fodor, Michel Meyer and Jean-Pascal Sutter|2017|Chem.-Eur.J.|23|11818|doi:10.1002/chem.201701732

CCDC 990046: Experimental Crystal Structure Determination

Related Article: Alexander Mitrofanov, Machima Manowong, Yoann Rousselin, Stéphane Brandès, Roger Guilard, Alla Bessmertnykh-Lemeune, Ping Chen, Karl M. Kadish, Nataliya Goulioukina, Irina Beletskaya|2014|Eur.J.Inorg.Chem.||3370|doi:10.1002/ejic.201402161

CCDC 993985: Experimental Crystal Structure Determination

Related Article: Nans Roques, Georges Mouchaham, Carine Duhayon, Stéphane Brandès, Aurélie Tachon, Guy Weber, Jean Pierre Bellat, Jean-Pascal Sutter|2014|Chem.-Eur.J.|20|11690|doi:10.1002/chem.201403638

CCDC 943452: Experimental Crystal Structure Determination

Related Article: Inhar Imaz, Georges Mouchaham, Nans Roques, Stéphane Brandès, and Jean-Pascal Sutter|2013|Inorg.Chem.|52|11237|doi:10.1021/ic401474f

CCDC 1985146: Experimental Crystal Structure Determination

Related Article: Adrien T. Normand, E. Daiann Sosa Carrizo, Corentin Magnoux, Esteban Lobato, Hélène Cattey, Philippe Richard, Stéphane Brandès, Charles H. Devillers, Anthony Romieu, Pierre Le Gendre, Paul Fleurat-Lessard|2021|Chemical Science|12|253|doi:10.1039/D0SC04736H

CCDC 1985142: Experimental Crystal Structure Determination

Related Article: Adrien T. Normand, E. Daiann Sosa Carrizo, Corentin Magnoux, Esteban Lobato, Hélène Cattey, Philippe Richard, Stéphane Brandès, Charles H. Devillers, Anthony Romieu, Pierre Le Gendre, Paul Fleurat-Lessard|2021|Chemical Science|12|253|doi:10.1039/D0SC04736H

CCDC 1985138: Experimental Crystal Structure Determination

Related Article: Adrien T. Normand, E. Daiann Sosa Carrizo, Corentin Magnoux, Esteban Lobato, Hélène Cattey, Philippe Richard, Stéphane Brandès, Charles H. Devillers, Anthony Romieu, Pierre Le Gendre, Paul Fleurat-Lessard|2021|Chemical Science|12|253|doi:10.1039/D0SC04736H

CCDC 1474154: Experimental Crystal Structure Determination

Related Article: Emmanuel Lerayer, Patrice Renaut, Stéphane Brandès, Hélène Cattey, Paul Fleurat-Lessard, Ghenwa Bouhadir, Didier Bourissou, and Jean-Cyrille Hierso|2017|Inorg.Chem.|56|1966|doi:10.1021/acs.inorgchem.6b02510

CCDC 1985136: Experimental Crystal Structure Determination

Related Article: Adrien T. Normand, E. Daiann Sosa Carrizo, Corentin Magnoux, Esteban Lobato, Hélène Cattey, Philippe Richard, Stéphane Brandès, Charles H. Devillers, Anthony Romieu, Pierre Le Gendre, Paul Fleurat-Lessard|2021|Chemical Science|12|253|doi:10.1039/D0SC04736H

CCDC 1875843: Experimental Crystal Structure Determination

Related Article: Oana Moncea, Juan Casanova-Chafer, Didier Poinsot, Lukas Ochmann, Clève D. Mboyi, Houssein O. Nasrallah, Eduard Llobet, Imen Makni, Molka El Atrous, Stéphane Brandès, Yoann Rousselin, Bruno Domenichini, Nicolas Nuns, Andrey A. Fokin, Peter R. Schreiner, Jean-Cyrille Hierso|2019|Angew.Chem.,Int.Ed.|58|9933|doi:10.1002/anie.201903089

CCDC 1880078: Experimental Crystal Structure Determination

Related Article: Wenqian Shan, Nicolas Desbois, Sandrine Pacquelet, Stéphane Brandès, Yoann Rousselin, Jeanet Conradie, Abhik Ghosh, Claude P. Gros, Karl M. Kadish|2019|Inorg.Chem.|58|7677|doi:10.1021/acs.inorgchem.8b03006

CCDC 943451: Experimental Crystal Structure Determination

Related Article: Inhar Imaz, Georges Mouchaham, Nans Roques, Stéphane Brandès, and Jean-Pascal Sutter|2013|Inorg.Chem.|52|11237|doi:10.1021/ic401474f

CCDC 1812155: Experimental Crystal Structure Determination

Related Article: Valentin Quesneau, Wenqian Shan, Nicolas Desbois, Stephane Brandes, Yoann Rousselin, Meddy Vanotti, Virginie Blondeau-Patissier, Mario Naitana, Paul Fleurat-Lessard, Eric Van Caemelbecke, Karl M. Kadish, Claude P. Gros|2018|Eur.J.Inorg.Chem.|2018|4265|doi:10.1002/ejic.201800897

CCDC 1871418: Experimental Crystal Structure Determination

Related Article: Adrien T. Normand, Quentin Bonnin, Stéphane Brandès, Philippe Richard, Paul Fleurat-Lessard, Charles H. Devillers, Cédric Balan, Pierre Le Gendre, Gerald Kehr, Gerhard Erker|2019|Chem.-Eur.J.|25|2803|doi:10.1002/chem.201805430

CCDC 993988: Experimental Crystal Structure Determination

Related Article: Nans Roques, Georges Mouchaham, Carine Duhayon, Stéphane Brandès, Aurélie Tachon, Guy Weber, Jean Pierre Bellat, Jean-Pascal Sutter|2014|Chem.-Eur.J.|20|11690|doi:10.1002/chem.201403638

CCDC 1871412: Experimental Crystal Structure Determination

Related Article: Adrien T. Normand, Quentin Bonnin, Stéphane Brandès, Philippe Richard, Paul Fleurat-Lessard, Charles H. Devillers, Cédric Balan, Pierre Le Gendre, Gerald Kehr, Gerhard Erker|2019|Chem.-Eur.J.|25|2803|doi:10.1002/chem.201805430

CCDC 1009948: Experimental Crystal Structure Determination

Related Article: Alexander Yu. Mitrofanov, Yoann Rousselin, Roger Guilard, Stéphane Brandès, Alla G. Bessmertnykh-Lemeune, Marina A. Uvarova, Sergey E. Nefedov|2016|New J.Chem.|40|5896|doi:10.1039/C5NJ03572D

CCDC 993987: Experimental Crystal Structure Determination

Related Article: Nans Roques, Georges Mouchaham, Carine Duhayon, Stéphane Brandès, Aurélie Tachon, Guy Weber, Jean Pierre Bellat, Jean-Pascal Sutter|2014|Chem.-Eur.J.|20|11690|doi:10.1002/chem.201403638

CCDC 1871414: Experimental Crystal Structure Determination

Related Article: Adrien T. Normand, Quentin Bonnin, Stéphane Brandès, Philippe Richard, Paul Fleurat-Lessard, Charles H. Devillers, Cédric Balan, Pierre Le Gendre, Gerald Kehr, Gerhard Erker|2019|Chem.-Eur.J.|25|2803|doi:10.1002/chem.201805430

CCDC 1402184: Experimental Crystal Structure Determination

Related Article: Georges Mouchaham, Marion Gualino, Nans Roques, Carine Duhayon, Stéphane Brandès, Jean-Pascal Sutter|2015|CrystEngComm|17|8906|doi:10.1039/C5CE01070E

CCDC 990049: Experimental Crystal Structure Determination

Related Article: Alexander Mitrofanov, Machima Manowong, Yoann Rousselin, Stéphane Brandès, Roger Guilard, Alla Bessmertnykh-Lemeune, Ping Chen, Karl M. Kadish, Nataliya Goulioukina, Irina Beletskaya|2014|Eur.J.Inorg.Chem.||3370|doi:10.1002/ejic.201402161

CCDC 1985140: Experimental Crystal Structure Determination

Related Article: Adrien T. Normand, E. Daiann Sosa Carrizo, Corentin Magnoux, Esteban Lobato, Hélène Cattey, Philippe Richard, Stéphane Brandès, Charles H. Devillers, Anthony Romieu, Pierre Le Gendre, Paul Fleurat-Lessard|2021|Chemical Science|12|253|doi:10.1039/D0SC04736H

CCDC 959781: Experimental Crystal Structure Determination

Related Article: Nikolay N. Makukhin, Nataliya S. Goulioukina, Alla G. Bessmertnykh-Lemeune, Stéphane Brandès, Roger Guilard, Irina P. Beletskaya|2015|Synthesis|47|279|doi:10.1055/s-0034-1378673

CCDC 993983: Experimental Crystal Structure Determination

Related Article: Nans Roques, Georges Mouchaham, Carine Duhayon, Stéphane Brandès, Aurélie Tachon, Guy Weber, Jean Pierre Bellat, Jean-Pascal Sutter|2014|Chem.-Eur.J.|20|11690|doi:10.1002/chem.201403638

CCDC 990047: Experimental Crystal Structure Determination

Related Article: Alexander Mitrofanov, Machima Manowong, Yoann Rousselin, Stéphane Brandès, Roger Guilard, Alla Bessmertnykh-Lemeune, Ping Chen, Karl M. Kadish, Nataliya Goulioukina, Irina Beletskaya|2014|Eur.J.Inorg.Chem.||3370|doi:10.1002/ejic.201402161

CCDC 993984: Experimental Crystal Structure Determination

Related Article: Nans Roques, Georges Mouchaham, Carine Duhayon, Stéphane Brandès, Aurélie Tachon, Guy Weber, Jean Pierre Bellat, Jean-Pascal Sutter|2014|Chem.-Eur.J.|20|11690|doi:10.1002/chem.201403638

CCDC 1537661: Experimental Crystal Structure Determination

Related Article: Georges Mouchaham, Nans Roques, Walid Khodja, Carine Duhayon, Yannick Coppel, Stéphane Brandès, Tamás Fodor, Michel Meyer and Jean-Pascal Sutter|2017|Chem.-Eur.J.|23|11818|doi:10.1002/chem.201701732

CCDC 943453: Experimental Crystal Structure Determination

Related Article: Inhar Imaz, Georges Mouchaham, Nans Roques, Stéphane Brandès, and Jean-Pascal Sutter|2013|Inorg.Chem.|52|11237|doi:10.1021/ic401474f

CCDC 1985143: Experimental Crystal Structure Determination

Related Article: Adrien T. Normand, E. Daiann Sosa Carrizo, Corentin Magnoux, Esteban Lobato, Hélène Cattey, Philippe Richard, Stéphane Brandès, Charles H. Devillers, Anthony Romieu, Pierre Le Gendre, Paul Fleurat-Lessard|2021|Chemical Science|12|253|doi:10.1039/D0SC04736H

CCDC 1042608: Experimental Crystal Structure Determination

Related Article: Stéphane Brandès, Alejandra Sornosa-Ten, Yoann Rousselin, Mickael Lagrelette, Christine Stern, Aurélien Moncomble, Jean-Paul Cornard, Michel Meyer|2015|J.Inorg.Biochem.|151|164|doi:10.1016/j.jinorgbio.2015.06.002

CCDC 1871411: Experimental Crystal Structure Determination

Related Article: Adrien T. Normand, Quentin Bonnin, Stéphane Brandès, Philippe Richard, Paul Fleurat-Lessard, Charles H. Devillers, Cédric Balan, Pierre Le Gendre, Gerald Kehr, Gerhard Erker|2019|Chem.-Eur.J.|25|2803|doi:10.1002/chem.201805430

CCDC 1537660: Experimental Crystal Structure Determination

Related Article: Georges Mouchaham, Nans Roques, Walid Khodja, Carine Duhayon, Yannick Coppel, Stéphane Brandès, Tamás Fodor, Michel Meyer and Jean-Pascal Sutter|2017|Chem.-Eur.J.|23|11818|doi:10.1002/chem.201701732

CCDC 990045: Experimental Crystal Structure Determination

Related Article: Alexander Mitrofanov, Machima Manowong, Yoann Rousselin, Stéphane Brandès, Roger Guilard, Alla Bessmertnykh-Lemeune, Ping Chen, Karl M. Kadish, Nataliya Goulioukina, Irina Beletskaya|2014|Eur.J.Inorg.Chem.||3370|doi:10.1002/ejic.201402161

CCDC 1537663: Experimental Crystal Structure Determination

Related Article: Georges Mouchaham, Nans Roques, Walid Khodja, Carine Duhayon, Yannick Coppel, Stéphane Brandès, Tamás Fodor, Michel Meyer and Jean-Pascal Sutter|2017|Chem.-Eur.J.|23|11818|doi:10.1002/chem.201701732

CCDC 1871409: Experimental Crystal Structure Determination

Related Article: Adrien T. Normand, Quentin Bonnin, Stéphane Brandès, Philippe Richard, Paul Fleurat-Lessard, Charles H. Devillers, Cédric Balan, Pierre Le Gendre, Gerald Kehr, Gerhard Erker|2019|Chem.-Eur.J.|25|2803|doi:10.1002/chem.201805430

CCDC 959780: Experimental Crystal Structure Determination

Related Article: Nikolay N. Makukhin, Nataliya S. Goulioukina, Alla G. Bessmertnykh-Lemeune, Stéphane Brandès, Roger Guilard, Irina P. Beletskaya|2015|Synthesis|47|279|doi:10.1055/s-0034-1378673

CCDC 960834: Experimental Crystal Structure Determination

Related Article: Alexander Yu. Mitrofanov, Yoann Rousselin, Roger Guilard, Stéphane Brandès, Alla G. Bessmertnykh-Lemeune, Marina A. Uvarova, Sergey E. Nefedov|2016|New J.Chem.|40|5896|doi:10.1039/C5NJ03572D

CCDC 1579042: Experimental Crystal Structure Determination

Related Article: Alejandra Sornosa-Ten, Pawel Jewula, Tamas Fodor, Stéphane Brandès, Vladimir Sladkov, Yoann Rousselin, Christine Stern, Jean-Claude Chambron, Michel Meyer|2018|New J.Chem.|42|7765|doi:10.1039/C8NJ00166A

CCDC 1402187: Experimental Crystal Structure Determination

Related Article: Georges Mouchaham, Marion Gualino, Nans Roques, Carine Duhayon, Stéphane Brandès, Jean-Pascal Sutter|2015|CrystEngComm|17|8906|doi:10.1039/C5CE01070E

CCDC 993986: Experimental Crystal Structure Determination

Related Article: Nans Roques, Georges Mouchaham, Carine Duhayon, Stéphane Brandès, Aurélie Tachon, Guy Weber, Jean Pierre Bellat, Jean-Pascal Sutter|2014|Chem.-Eur.J.|20|11690|doi:10.1002/chem.201403638

CCDC 1871417: Experimental Crystal Structure Determination

Related Article: Adrien T. Normand, Quentin Bonnin, Stéphane Brandès, Philippe Richard, Paul Fleurat-Lessard, Charles H. Devillers, Cédric Balan, Pierre Le Gendre, Gerald Kehr, Gerhard Erker|2019|Chem.-Eur.J.|25|2803|doi:10.1002/chem.201805430

CCDC 1009991: Experimental Crystal Structure Determination

Related Article: Alexander Yu. Mitrofanov, Yoann Rousselin, Roger Guilard, Stéphane Brandès, Alla G. Bessmertnykh-Lemeune, Marina A. Uvarova, Sergey E. Nefedov|2016|New J.Chem.|40|5896|doi:10.1039/C5NJ03572D

CCDC 990048: Experimental Crystal Structure Determination

Related Article: Alexander Mitrofanov, Machima Manowong, Yoann Rousselin, Stéphane Brandès, Roger Guilard, Alla Bessmertnykh-Lemeune, Ping Chen, Karl M. Kadish, Nataliya Goulioukina, Irina Beletskaya|2014|Eur.J.Inorg.Chem.||3370|doi:10.1002/ejic.201402161

CCDC 1985135: Experimental Crystal Structure Determination

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CCDC 1985137: Experimental Crystal Structure Determination

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