Nanoporous materials: a good opportunity for nanosciences

Corriu, Robert J. P.; Mehdi, Ahmad; Reyé, Catherine

doi:10.1016/j.jorganchem.2004.07.064

Cited by 35 publications

(15 citation statements)

References 121 publications

(120 reference statements)

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“…To rationalise this observation, we assumed that an approximately constant number of sites could accommodate moieties of approximately the same molecular mass. After several attempts to aggregate the different chemical entities H 2 From the results (Table 1), the sum (q + r + s) is not rigorously constant as initially assumed but changes slowly, as the mass of the extra-framework does not vary much. The actual framework and extra-framework formulae have been written for each sub-ensemble in a neutral form.…”

Section: Resultsmentioning

confidence: 98%

See 1 more Smart Citation

The Extra‐Framework Sub‐Lattice of the Metal–Organic Framework MIL‐110: A Solid‐State NMR Investigation

Haouas

Volkringer

Loiseau

et al. 2009

Chemistry A European J

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A changeable character: Differences in the dynamics of occluded moieties within the large pores (see graphic) of aluminium 1,3,5-benzene tricarboxylate framework solid MIL-110 are a function of the synthesis pH. Host-guest proton-transfer processes lead to a reversible change in the character of the framework from cationic to neutral, depending on the nature of the extra-framework moieties.The aluminium 1,3,5-benzene tricarboxylate framework solid MIL-110, which crystallises either at pH approximately 0 or at pH approximately 4, has been investigated by solid-state NMR spectroscopy. At pH approximately 0 the solid (MIL-110{pH0}) is the unique stable thermodynamic product, whereas at pH approximately 4 MIL-110{pH4} is observed as a kinetic product in competition with the MIL-96 phase. Diffraction studies and (27)Al NMR spectroscopy prove that the framework is identical in both cases. The nature and dynamics of occluded moieties within the large pores look quite different for the two compounds. MIL-110{pH4} and MIL-110{pH0} both show the presence of occluded 1,3,5-benzene tricarboxylate (btc), with additional nitrates and water molecules. However, the proportions of btc, nitrates and water are functions of the pH, leading to an identical framework and a quite different extra-framework. With the extra-framework moieties, the framework undergoes a proton transfer which is a function of the synthesis pH. Washing the MIL-110{pH0} phase with water produces a different extra-framework structure, richer in water and poorer in btc and nitrates. The hydroxyl groups of the inorganic aluminium cluster of the framework are involved in a proton transfer, which leads for all cases to a cationic framework and an anionic extra-framework. (1)H-(1)H DQ 2D NMR spectra (DQ=double quantum) give evidence for the interaction of extra-framework btc with the terminal water carried by Al(2,3) and shows their proximity to the closest hydroxyl groups. A structure for the non-diffracting extra-framework is proposed as the most plausible topology. It provides an efficient picture for the creation of many substituted MIL-110 compounds that would have a large number of applications.

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Section: Resultsmentioning

confidence: 98%

“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] They are interesting for their sorption, magnetic and optical properties and currently involve di-and trivalent metals. Among the latter, aluminium takes a special place.…”

Section: Introductionmentioning

confidence: 99%

The Extra‐Framework Sub‐Lattice of the Metal–Organic Framework MIL‐110: A Solid‐State NMR Investigation

Haouas

Volkringer

Loiseau

et al. 2009

Chemistry A European J

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“…them ranging from catalysis to food science. [9][10][11][12][13][14][15][16][17][18][19][20][21][22][23] The excitement about the construction of nanosized devices, and especially those using single molecules, [24] stems in part from the fact that they represent the logical endpoint for the ongoing miniaturization of devices, for example, of the integrated circuits in computers, which underlies the whole electronics revolution that has changed the face of our world. As Richard Feynman famously pointed out, [25] if 100 atoms were sufficient to store one bit (binary digit) of information then all the books ever written could be stored in a cube with edges 6 mm long, so the potential impact of nanotechnology on information storage and processing is hard to overstate.…”

Section: Introductionmentioning

confidence: 99%

The Chemistry of Organic Nanomaterials

2005

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The development of nanotechnology using organic materials is one of the most intellectually and commercially exciting stories of our times. Advances in synthetic chemistry and in methods for the investigation and manipulation of individual molecules and small ensembles of molecules have produced major advances in the field of organic nanomaterials. The new insights into the optical and electronic properties of molecules obtained by means of single-molecule spectroscopy and scanning probe microscopy have spurred chemists to conceive and make novel molecular and supramolecular designs. Methods have also been sought to exploit the properties of these materials in optoelectronic devices, and prototypes and models for new nanoscale devices have been demonstrated. This Review aims to show how the interaction between synthetic chemistry and spectroscopy has driven the field of organic nanomaterials forward towards the ultimate goal of new technology.

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“…Additionally, the carried out synthesis methods are able to draw innovating architectures, where the active groups are located either in the channels or constitute a part of the silica backbone [20]. A functionalization of the silica pores can be performed either by grafting the active molecules to the silica channels walls using organosilica chains or by direct synthesis methods [21]. In this case, the functional groups are expected to be more regularly distributed in the channels leading to a homogeneous media.…”

Section: Introductionmentioning

confidence: 99%

Mesoporous Silica Functionalized by Cyclam–Metal Groups: Spectroscopic Studies and Numerical Modeling

Makowska‐Janusik

Kassiba

Errien

et al. 2010

J Inorg Organomet Polym

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Mesoporous silica functionalized by cyclammetal molecules were investigated by spectroscopic methods including Raman, IR, UV-VIS absorption and EPR technique. To analyse quantitatively the physical features, numerical models were developed using the density functional theory method. Thus, the construction of molecular geometries and their optimisation analysis were achieved on the cyclam-metal molecules in vacuum as well as constrained by the host mesoporous silica matrixes. In this context and with regard to the paramagnetic nature of the metals chelated by cyclam molecules, EPR technique allows probing the metal environments which can be compared to theoretical results inferred from numerical models. The vibrational and optical properties were exhaustively investigated and the assignment of the main features was quantitatively discussed thanks to the carried out numerical analyses. The developed approach point out the possibility to define a targeted application of such functional materials based on the possibility to fine tune the absorption features in a wide wavelength range by stabilizing defined configurations of the cyclam-metal groups.

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Nanoporous materials: a good opportunity for nanosciences

Cited by 35 publications

References 121 publications

The Extra‐Framework Sub‐Lattice of the Metal–Organic Framework MIL‐110: A Solid‐State NMR Investigation

The Extra‐Framework Sub‐Lattice of the Metal–Organic Framework MIL‐110: A Solid‐State NMR Investigation

The Chemistry of Organic Nanomaterials

Mesoporous Silica Functionalized by Cyclam–Metal Groups: Spectroscopic Studies and Numerical Modeling

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