Stéphane Brandès

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 method gave rise to hexagonally ordered mesoporous hybrid materials. The second afforded mesoporous hybrid materials with a typically disordered wormhole-like framework structure in which the organic groups are probably regularly distributed. The O2-binding capacity of Co-fluomine immobilized on these materials via the imidazole group was investigated.

Metallocorroles as sensing components for gas sensors: remarkable affinity and selectivity of cobalt(III) corroles for CO vs. O2 and N2

Most commercially available CO detectors are based upon metal oxides or electrochemical cell technologies. None of these approaches use the selective adsorption of CO gas on a molecular complex. Conversely, cobalt(III) corroles can bind small gaseous molecules allowing them for an application as sensing components for gas detectors. Here we describe the ability of cobalt corroles to selectively coordinate carbon monoxide vs. dinitrogen and dioxygen. The coordination properties were determined in the solid state and the adsorption characteristics were compared to those of the reference compound (To-PivPP)Fe(1,2-Me2Im), known for its remarkable CO binding properties. The adsorption data evidence that the selectivity, affinity and capacity of the cobalt(III) corroles for CO are larger than those of the porphyrin complex. However, from a chemical point of view, the selectivity of cobalt(III) corroles for CO vs. O2 is infinite since these derivatives do not bind O2 while (To-PivPP)Fe(1,2-Me2Im) does with an M value (PO2(1/2)/PCO(1/2)) equal to 51. In this manuscript we also show that the affinity of cobalt(III) corroles for CO is closely related to the Lewis acid character of the central cobalt(III) ion and therefore to the nature of the substituents at the periphery of the corrole macroring.

Cyclam complexes containing silica gels for dioxygen adsorption

Several cyclam incorporating silica gels have been synthesised using three different methods, including a sol–gel approach. These various materials show different textures and the macrocycle contents can reach values up to 1.5 mmol g−1. Cu(II) and Co(II) complexes of these modified silica gels have been studied. Finally, the efficiency of [Co(cyclam)]2+ grafted onto silica for binding dioxygen has been determined using ESR spectroscopy and static volumetric gas uptake measurements. The most efficient material behaves as a high-performance dioxygen binding system, showing a very high affinity for dioxygen ((P1/2)1 = 1.91 Torr) coupled with a large total volume of gas adsorbed at 1 atm (3.0 cm3 g−1).

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 and a flexible cyclic polyaminocarboxylate. We have demonstrated, for the first time, that a porous rigid framework can be obtained by starting from a flexible amine building block. Sorption measurements revealed that the material exhibited a high surface area (135 m(2) g(-1)) and was the best compromise between capacity and selectivity for CO(2) over CO, CH(4), N(2) and O(2); as such it is a promising new selective adsorbent for CO(2) capture.

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 cyclam groups with respect to solution-phase Cu(II), suggesting lower stability of immobilized complexes relative to those in solution. Therefore, the number of arms attaching cyclam moieties to the silica walls (one, two, or four) was found to dramatically affect the binding properties of these hybrids toward copper(II), revealing significantly larger capacities when reducing the number of arms (less rigidity constraints in the macrocycle). In parallel, multiarm tethering resulted in better chemical resistance toward degradation as evidenced by UV-visible monitoring of Cu-cyclam complexes in solution (i.e., more ligand leaching from the adsorbent for singly tethered cyclam). On the other hand, electron spin resonance (ESR) experiments did not evidence significant differences between complexes bearing one, two, or four alkyl arms, since all Cu(II)-cyclam surface complexes were found to be hexacoordinated with a strong equatorial ligand field. Comparison of amorphous gels and mesostructured materials indicates that the binding properties of the adsorbents were hardly influenced by their level of ordering, suggesting that accessibility to the binding sites was not the limiting factor. Some advantage belonging to mesostructured adsorbents was however observed with respect to the rate of access to the active centers at pH values close to neutrality (due to faster mass transport), but this was no more the case when operating at lower pH values where the formation of the Cu-cyclam complex became the rate-determining step, as pointed out by electrochemistry.

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.

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.

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 reactions, and good agreement has been observed between the theoretical predictions and experimental data. 1D- and 2D-NMR studies reveal a highly rigid structure in the case of macrobicycles. The macropolycyclic ligands show very different basicities, which demonstrates the influence of the cross-linker on the coordination properties of the ligands.

NEW SILICA-GEL-BOUND POLYAZACYCLOALKANES AND CHARACTERIZATION OF THEIR COPPER(II) COMPLEXES USING ELECTRON SPIN RESONANCE SPECTROSCOPY

Several tetraazamacrocycle-bonded silica gels have been synthesized and characterized. 1,4,7,10-Tetraazacyclododecane, 1,4,8,11-tetraazacyclotetradecane and 1,5,9,13-tetraazacyclohexadecane have been covalently bound to silica gel and their respective copper(II) complexes characterized. Three different methods were used for capacity determinations: quantitative ESR measurements of copper(II) complexes, nitrogen, carbon and copper elemental analysis and UV/VIS measurements.

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 K4[Zr(CA)4], where DBQ(2-) and CA(2-) 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 show that the framework breathing occurs only when a slight gas pressure is applied. Crystal structures for both the hydrated and guest free phases of K4[Zr(DBQ)4] have been investigated.