Switchable Surface Hydrophobicity–Hydrophilicity of a Metal–Organic Framework

Rodríguez‐Hermida, Sabina; Tsang, Min Ying; Vignatti, Claudia; Stylianou, Kyriakos C.; Guillerm, Vincent; Pérez‐Carvajal, Javier; Teixidor, Francesc; Viñas, Clara; Choquesillo‐Lazarte, Duane; Verdugo‐Escamilla, Cristóbal; Peral, Inma; Juanhuix, Jordi; Verdaguer, Albert; Imaz, Inhar; Maspoch, Daniel; Planas, José Giner

doi:10.1002/ange.201609295

Cited by 12 publications

(14 citation statements)

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“…The syn ‐diastereoisomer of 1,2‐bis[(pyridin‐3‐yl)methanol]‐1,2‐dicarba‐ closo ‐dodecaborane ( 1 ) was synthesized according to the reported method. [9c] FTIR ATR spectra were recorded with a Perkin–Elmer Spectrum One spectrometer. The 1 H and 11 B spectra were recorded at 300 and 96 MHz, respectively, with a Bruker Advance‐300 spectrometer in deuterated DMSO, unless denoted, and were referenced to the residual solvent peak for 1 H and 13 C{ 1 H} NMR or to BF 3 OEt 2 as the external standard for 11 B NMR spectroscopy.…”

Section: Methodsmentioning

confidence: 99%

“…The host compound presented in this paper belongs to the Pd 2 L 2 ‐type metallacycles, but it has a building unit distinct from those of the previously mentioned metallacycles. In particular, it contains a disubstituted o ‐carboranyl alcohol, bearing two 3‐pyridyl moieties ( 1 in Figure ) . The high thermal and chemical stability, hydrophobicity, acceptor character, ease of functionalization, and three‐dimensional nature of the icosahedral carborane clusters ( closo ‐C 2 B 10 H 12 ) make these new molecules valuable ligands in chemistry and materials science .…”

Section: Introductionmentioning

confidence: 99%

“…[10f], We have been particularly interested in relating the field of molecular crystal engineering with that of icosahedral carboranes. [9b], [9c], [11a], It is surprising that, taking into account the rich supramolecular chemistry and bulkiness of icosahedral carborane derivatives, crystalline lattice‐inclusion compounds have been hardly reported. [11i], Compound 1 , which is prepared in very good yield from one‐pot reactions and from readily available starting materials,[10a] is centered on an o ‐carborane core with one or two arms radiating out of one of the cluster carbons, containing a carbon that bears an alcohol and a 3‐pyridyl moiety.…”

Section: Introductionmentioning

confidence: 99%

“…[11i], Compound 1 , which is prepared in very good yield from one‐pot reactions and from readily available starting materials,[10a] is centered on an o ‐carborane core with one or two arms radiating out of one of the cluster carbons, containing a carbon that bears an alcohol and a 3‐pyridyl moiety. The arrangement of the pyridyl moieties in this compound, from the single‐crystal X‐ray diffraction structural analysis,[9c] suggests that it could act as a bidentate ligand for the construction of metallacyclic structures. [12b], The lower symmetry (Cs) and awkward shape of our carboranyl ligand, compared with most of the reported bidentate pyridines (C 2 symmetry), could provide lower symmetry and a more awkward shape of the corresponding Pd 2 L 2 ‐type metallacycles, and therefore, inclusion properties.…”

Section: Introductionmentioning

confidence: 99%

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Crystalline Inclusion Compounds of a Palladacyclic Tetraol Host Featuring o‐Carborane Units

et al. 2017

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Crystalline Inclusion Compounds of a Palladacyclic Tetraol Host Featuring o‐Carborane Units

et al. 2017

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“…In order to prepare hydrophobic MOFs, Planas et al used an orthocarborane functionalized with pyridylmethyl alcohol groups at the C-positions as a hydrophobic linker to Zn-1,4-benzenedicarboxylate [58]. Moreover, the substrate could change from highly hydrophobic to superhydrophilic by immersion in NaOH/DMF.…”

Section: Guestmentioning

confidence: 99%

Switchable and Reversible Superhydrophobic Surfaces: Part Two

Taleb¹,

Darmanin²,

Guittard³

2018

Interdisciplinary Expansions in Engineering and Design With the Power of Biomimicry

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In this book chapter, most of the methods used in the literature to prepare switchable and reversible superhydrophobic surfaces are described. Inspired by Nature, it is possible to induce the Cassie-Baxter-Wenzel transition using different external stimuli such as light, temperature, pH, ion exchange, voltage, magnetic field, mechanic stress, plasma, ultrasonication, solvent, gas or guest. Such properties are extremely important for various applications but especially for controllable oil/water separation membranes, oil-absorbing materials, and water harvesting systems.Keywords: superhydrophobic, reversible, switchable, bioinspiration, biomimetism Reversible superhydrophobic surfaces: Part twoThis section provides continuation of the description of the stimuli used in the literature to induce reversible changes in surface wettability. Ion exchangeSince 2004, the researchers have shown that the presence of charged species such as quaternary ammonium groups are sensitive to ion exchange and lead to different surface wettabilities. In 2004, Choi et al. prepared self-assembled monolayers (SAM) with imidazolium groups on smooth Au and Si/SiO 2 substrates [1][2][3]. They studied the effect of a series of anions as shown in Figure 1 and In order to elaborate reversible superhydrophobic properties by ion exchange, gold micro and nanostructured substrates were performed by electroless etching process by immersing silicon substrates in aqueous solution of HAuCl 4 and HF (Figure 2). The surface was then modified by SAM using a thiol terminated by a quaternary ammonium. Then, the surface wettability could be reversely changed from superhydrophilic to superhydrophobic after [20]. Here, the presence of TSPM (sol-gel precursor) was used not only to form a polymer network via intramolecular interactions but also to anchor substrates (Figure 3). The membranes could reversely change from superhydrophobic/highly oleophobic to superhydrophilic/superoleophobic after exchanging Cl − ions by heptadecafluorooctanesulfonic acid (C 8 F 17 SO 3 − or HPS − ) ions. Moreover, the membranes were also highly efficient filter medium for removing multiple contaminants such as SO 2 form waster gas streams. A nother strategy was to deposit polyelectrolyte multilayers poly(diallyldimethylammonium chloride (PDDA) and poly(sodium 4-styrenesulfonate) (PSS) on gold micro and nanostructured substrates [21]. The authors studied the influence of the exchanged ions and the highest properties were obtained by exchanging Cl − (θ w < 5°) ions by PFO − (θ w = 164°). The authors also deposited polyelectrolyte multilayers on micro and nanostructured aluminum substrates obtained by etching in HCl and immersion in boiling water [22,23]. Using PFO − ions, the substrates were superhydrophobic and superoleophobic. When the substrates were immersed in seawater, the PFO − ions were exchanged by hydrophilic Cl − or SO 4 2− making the substrates underwater superoleophobic. Magnetic fieldEnvironment protection against oil leakage during oil tankers sinking is ...

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A Metal‐Organic Framework Incorporating Eight Different Size Rare‐Earth Metal Elements: Toward Multifunctionality À La Carte

Light

et al. 2023

Adv Funct Materials

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Multi‐metallic multivariate (MTV) rare earth (RE) metal−organic frameworks (MOFs) are of interest for the development of multifunctional materials, however examples with more than three RE cations are rare and obstructed by compositional segregation during synthesis. Herein, this work demonstrates the synthesis of a multi‐metallic MTV RE MOF incorporating two, four, six, or eight different RE ions with different sizes and in nearly equimolar amounts and no compositional segregation. The MOFs are formed by a combination of RE cations (La, Ce, Eu, Gd, Tb, Dy, Y, and Yb) and a 1,7‐di(4‐carboxyphenyl)‐1,7‐dicarba‐closo‐dodecaborane (mCB‐L) linker. The steric bulkiness and acidity of mCB‐L is crucial for the incorporation of different size RE ions into the MOF structure. Demonstration of the incorporation of all RE cations is performed via compositional and structural characterization. The more complex MTV MOF, including all eight RE ions (mCB‐8RE), are also characterized using optical, thermal, and magnetic techniques. Element‐selective X‐ray absorption spectroscopy and X‐ray Magnetic Circular Dichroism measurements allow us to characterize spectroscopically each of the eight RE ions and determine their magnetic moments. This work paves the way for the investigation of MTV MOFs with the possibility to combine RE ions à la carte for diverse applications.

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Switchable Surface Hydrophobicity–Hydrophilicity of a Metal–Organic Framework

Cited by 12 publications

References 49 publications

Crystalline Inclusion Compounds of a Palladacyclic Tetraol Host Featuring o‐Carborane Units

Crystalline Inclusion Compounds of a Palladacyclic Tetraol Host Featuring o‐Carborane Units

Switchable and Reversible Superhydrophobic Surfaces: Part Two

A Metal‐Organic Framework Incorporating Eight Different Size Rare‐Earth Metal Elements: Toward Multifunctionality À La Carte

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