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Covalent organic frameworks (COFs) are an emerging material family having several potential applications. Their porous framework and redox-active centers enable gas/ion adsorption, allowing them to function as safe, cheap, and tunable electrode materials in next-generation batteries, as well as CO2 adsorption materials for carbon-capture applications. Herein, we develop four polyimide COFs by combining aromatic triamines with aromatic dianhydrides and provide detailed structural and electrochemical characterization. Through density functional theory (DFT) calculations and powder X-ray diffraction, we achieve a detailed structural characterization, where DFT calculations reveal that the imide bonds prefer to form at an angle with one another, breaking the 2D symmetry, which shrinks the pore width and elongates the pore walls. The eclipsed perpendicular stacking is preferable, while sliding of the COF sheets is energetically accessible in a relatively flat energy landscape with a few metastable regions. We investigate the potential use of these COFs in CO2 adsorption and electrochemical applications. The adsorption and electrochemical properties are related to the structural and chemical characteristics of each COF, giving new insights for advanced material designs. For CO2 adsorption specifically, the two best performing COFs originated from the same triamine building block, which-in combination with force-field calculations-revealed unexpected structure-property relationships. Specific geometries provide a useful framework for Na-ion intercalation with retainable capacities and stable cycle life at a relatively high working potential (>1.5 V vs Na/Na+). Although this capacity is low compared to conventional inorganic Li-ion materials, we show as a proof of principle that these COFs are especially promising for sustainable, safe, and stable Na-aqueous batteries due to the combination of their working potentials and their insoluble nature in water.

The ease with which molecular building blocks can be ordered in metal–organic frameworks is an invaluable asset for many potential applications. In this work, we exploit this inherent order to produce chromatic polarizers based on visible-light linear dichroism via cobalt paddlewheel chromophores.

International audience; The organic components in metal−organic frameworks (MOFs) are unique: they are embedded in a crystalline lattice, yet, as they are separated from each other by tunable free space, a large variety of dynamic behavior can emerge. These rotational dynamics of the organic linkers are especially important due to their influence over properties such as gas adsorption and kinetics of guest release. To fully exploit linker rotation, such as in the form of molecular machines, it is necessary to engineer correlated linker dynamics to achieve their cooperative functional motion. Here, we show that for MIL-53, a topology with closely spaced rotors, the phenylene functionalization allows researchers to tune the rotors' steric environment, shifting linker rotation from completely static to rapid motions at frequencies above 100 MHz. For steric interactions that start to inhibit independent rotor motion, we identify for the first time the emergence of coupled rotation modes in linker dynamics. These findings pave the way for function-specific engineering of gear-like cooperative motion in MOFs.

p-Nitroaniline presents the typical motif of a second-order nonlinear optically (NLO) active molecule. However, because of its crystallization in an antiparallel and hence centrosymmetric structure, the NLO activity is lost. In this contribution, the p-nitroaniline motif was built successfully into the MIL-53 metal-organic framework. More precisely, MIL-53 was synthesized with 2-amino-5-nitroterephthalate as organic linker, with Al3+, Ga3+, or In3+ as inorganic cation. The Al and Ga structures are polar, as confirmed by second-harmonic generation microscopy, yielding stable NLO materials. Indeed, they contain a 22-36% surplus of the dipolar 2-amino-5-nitro-terephthalate oriented in a parallel fashion. The indium compound was shown to be less crystalline and centrosymmetric. Ab initio modeling of the second-order NLO response shows that the Al and Ga materials show a response comparable to typical inorganic commercial NLO materials such as KDP. As a hybrid material, capable of low-temperature synthesis and processing and the ultrafast NLO responses associated with organic materials, this material can potentially provide an interesting venue for applications with respect to traditional inorganic NLO materials. ispartof: Journal of Physical Chemistry C vol:121 issue:45 pages:25509-25519 ispartof: location:United States status: published

We report the potential-dependent interactions of trimesic acid with Cu surfaces in EtOH. CV experiments and electrochemical surface-enhanced Raman spectroscopy show the presence of an adsorbed trimesic acid layer on Cu at potentials lower than 0 V vs Cu. The BTC coverage increases as the potential increases, reaching a maximum at 0 V. Based on molecular dynamics simulations, we report adsorption geometries and possible structures of the organic adlayer. We find that, depending on the crystal facet, trimesic acid adsorbs either flat or with one or two of the carboxyl groups facing the metal surface. At higher coverages, a multi-layer forms that is composed mostly of flat-lying trimesic acid molecules. Increasing the potential beyond 0 V activates the Cu-adsorbate interface in such a way that under oxidation of Cu to Cu2 +, a 3-D metal-organic framework forms directly on the electrode surface. PS gratefully acknowledges the Max Planck Graduate Center and the Studienstiftung des deutschen Volkes for the funding. KFD gratefully acknowledges the generous funding through the Emmy Noether program of the Deutsche Forschungsgemeinschaft (DO 1691/1-1).

The surface-induced polymerization of a chromophore-functionalized monomer was probed in situ for the first time using a nonlinear optical technique, second-harmonic generation. During the first hours of the polymerization reaction, dramatic changes in the tilt angle of the chromophore-functionalized side groups were observed. Following evaluation of the nonlinear optical data with those obtained from atomic force microscopy and ultraviolet-visible, we conclude that second-harmonic generation efficiently probes the polymerization reaction and the conformational changes of the surface-grafted polymer. With polymerization time, the conformation of the surface-tethered polymer changes from a conformation with the polymer backbone and its side groups flat on the surface, i.e., a "pancake" conformation, to a conformation where the polymer backbone is stretched away combined with tilted side groups or an enlarged tilt angle distribution, i.e., a "brush-type" conformation.

In this work we present a comprehensive experimental study to determine the contact forces between individual metal oxide nanoparticles in the gas-phase using atomic force microscopy. In addition, we determined the amount of physisorbed water for each type of particle surface. By comparing our results with mathematical models of the interaction forces, we could demonstrate that classical continuum models of van der Waals and capillary forces alone cannot sufficiently describe the experimental findings. Rather, the discrete nature of the molecules has to be considered, which leads to ordering at the interface and the occurrence of solvation forces. We demonstrate that inclusion of solvation forces in the model leads to quantitative agreement with experimental data and that tuning of the molecular order by addition of isopropanol vapor allows us to control the interaction forces between the nanoparticles.

A modulated synthesis approach based on the chelating properties of oxalic acid (H2C2O4) is presented as a robust and versatile method to achieve highly crystalline Al‐based metal‐organic frameworks. A comparative study on this method and the already established modulation by hydrofluoric acid was conducted using MIL‐53 as test system. The superior performance of oxalic acid modulation in terms of crystallinity and absence of undesired impurities is explained by assessing the coordination modes of the two modulators and the structural features of the product. The validity of our approach was confirmed for a diverse set of Al‐MOFs, namely X‐MIL‐53 (X=OH, CH3O, Br, NO2), CAU‐10, MIL‐69, and Al(OH)ndc (ndc=1,4‐naphtalenedicarboxylate), highlighting the potential benefits of extending the use of this modulator to other coordination materials., The chelation of aluminium ions by oxalic acid enables a versatile modulation action, drastically increasing crystal size without undesired framework modifications.

Metal-organic framework ZIF-8, from the zeolitic imidazolate framework family, shows a large intrinsic second-order nonlinear optical (NLO) response. In addition, ZIF-8 is a stable, inexpensive material that is transparent in the visible (vis) and near-infrared (NIR) window. This is crucial for NLO applications. The second-order NLO activity is due to the noncentrosymmetric octupolar symmetry of the material. We found that fast syntheses lead to a lower second-order NLO response. Consistent with polarized second-harmonic generation (SHG) microscopy measurements, we ascribe this to defects that create local centers of centrosymmetry but do not affect the orientation of the crystal lattice. Syntheses with slow nucleation lead to quasi-perfect crystals with a large average second-order NLO coefficient 〈deff〉 of 0.25 pm/V, which is explained and supported by ab initio theoretical calculations.

Development of state-of-the-art selective adsorbent materials for recovery of rare earth elements (REEs) is essential for their sustainable usage. In this study, a metal-organic framework (MOF), MIL-101(Cr), was synthesized and post-synthetically modified with optimised loading of the organophosphorus compounds tributyl phosphate (TBP), bis(2-ethylhexyl) hydrogen phosphate (D2EHPA, HDEHP) and bis(2,4,4-trimethylpentyl) phosphinic acid (Cyanex®-272). The materials were characterized and their adsorption efficiency towards Nd3+, Gd3+ and Er3+ from aqueous solutions was investigated. The MOF derivatives demonstrated an increase in adsorption capacity for Er3+ at optimal pH 5.5 in the order of MIL-101-T50 (37.2 mg g−1) < MIL-101-C50 (48.9 mg g−1) < MIL-101-H50 (57.5 mg g−1). The exceptional selectivity of the materials for Er3+ against transition metal ions was over 90%, and up to 95% in the mixtures with rare earth ions. MIL-101-C50 and MIL-101-H50 demonstrated better chemical stability than MIL-101-T50 over 3 adsorption−desorption cycles. The adsorption mechanism was described by the formation of coordinative complexes between the functional groups of modifiers and Er3+ ions.

International audience; Among the numerous fascinating properties of metal–organic frameworks (MOFs), their rotational dynamics is perhaps one of the most intriguing, with clear consequences for adsorption and separation of molecules, as well as for optical and mechanical properties. A closer look at the rotational mobility in MOF linkers reveals that it is not only a considerably widespread phenomenon, but also a fairly diverse one. Still, the impact of these dynamics is often understated. In this review, we address the various mechanisms of linker rotation reported in the growing collection of literature, followed by a highlight of the methods currently used in their study, and we conclude with the impacts that such dynamics have on existing and future applications.

Recent developments in nonlinear optical light scattering techniques have opened a window into morphological and structural characteristics for a variety of supramolecular systems. However, for the study of dynamic processes, the current way of measuring is often too slow. Here we present an alternative measurement scheme suitable for following dynamic processes. Fast acquisition times are achieved through Fourier imaging, allowing simultaneous detection at multiple scattering angles for different polarization combinations. This allows us to follow the crystal growth of the metal organic framework ZIF-8 in solution. The angle dependence of the signal provides insight into the growth mechanism by probing the evolution of size, shape and concentration, while polarization analysis yields structural information in terms of point group symmetry. Our findings highlight the potential of dynamic angle-resolved harmonic light scattering to probe crystal growth processes, assembly–disassembly of biological systems, adsorption, transport through membranes and myriad other applications., Angle-resolved monitoring of structure parameters during crystal growth is often slow owing to mechanical movements. Here, the authors use second harmonic scattering and Fourier-plane imaging to dynamically monitor size, shape and concentration of ZIF-8 in situ during the growth process.

© 2016 The Royal Society of Chemistry. Aluminium isophthalate CAU-10-H [Al(OH)(benzene-1,3-dicarboxylate)]·nH2O exhibits water adsorption characteristics which make it a promising adsorbent for application in heat-exchange processes. Herein we prepared a stable coating of this MOF and evaluated its long-term stability under closed-cycle conditions for 10000 water adsorption and desorption cycles, which are typical lifetimes for adsorption heat storage (AHS) applications. No degradation of the adsorption capacity could be observed which makes CAU-10-H the most stable MOF under these humid cycling conditions reported until now. Moreover, thermophysical properties like thermal conductivity and heat of adsorption were directly measured. In order to identify the structural features associated with the adsorption behaviour, the structural differences between the dry and the water loaded CAU-10-H were studied by Rietveld refinements and second harmonic generation (SHG) microscopy. The observed transition of space group symmetry from I41 to I41/amd between the humid and dry forms is induced by the adsorption/desorption of water into/out of the MOF channels. This originates from a torsional motion around the C-C bond between the carboxylate groups and the aromatic ring in half of the linker molecules. These observations are in excellent agreement with molecular dynamics simulations which confirm the energetic benefit of this transition. crosscheck: This document is CrossCheck deposited related_data: Supplementary Information related_data: Crystal Structure Data identifier: Karen Markey (ORCID) copyright_licence: The Royal Society of Chemistry has an exclusive publication licence for this journal copyright_licence: This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0) history: Received 27 February 2016; Accepted 27 June 2016; Accepted Manuscript published 28 June 2016; Advance Article published 13 July 2016; Version of Record published 26 July 2016 ispartof: Journal of Materials Chemistry A vol:4 issue:30 pages:11859-11869 status: published

The inclusion of Ti(IV) in water-stable metal-organic frameworks has been proposed as a strategy for the generation of high surface area heterogeneous photocatalysts, with UiO-66 being a promising candidate. We find that the site of binding of Ti(IV) is at linker defect sites and not incorporated into the inorganic secondary building unit through metal exchange. We also demonstrate the choice of titanium source is critical in the generation of an active hydrogen evolution catalyst, and explain the observed activity using density functional theory calculations, which also enable rational design of future Ti(IV) coordination environments in MOF catalysts

The room temperature growth kinetics of the commonly studied metal-organic framework CuBTC (HKUST-1) is investigated with UV/vis absorption spectroscopy. Contrary to chemical intuition, increased concentrations of the BTC ligand slows down the formation of CuBTC. Based on the time-resolved experimental data, a kinetic model is proposed for CuBTC growth. This model is based on a chemical reaction equation sequence for the production of CuBTC including an overcoordinated, slowly reacting Cu-BTCx species. This growth model excellently captures the temporal CuBTC development over the entire range of concentration conditions.

Polar metal–organic frameworks have potential applications as functional non-linear optical, piezoelectric, pyroelectric and ferroelectric materials. Using second harmonic generation microscopy we found that fluoride doping of the microporous iron(III) terephthalate MOF MIL-53(Fe) induces a polar organization in its structure, which was not previously detected with XRD. The polar order is only observed when both fluoride and guest molecules are present, and may be related to a complex interplay between the adsorbates and the framework, leading to a modification of the positioning of fluoride in the inorganic Fe-chains. Combined polarized second harmonic generation microscopy and scanning pyroelectric microscopy show that the polar axis is unidirectional and of the same sense over the whole crystal, extending up to 100 micrometers. This finding shows how MOF materials can be endowed with useful properties by doping MOFs with fluoride. crosscheck: This document is CrossCheck deposited related_data: Supplementary Information identifier: Karen Markey (ORCID) copyright_licence: The Royal Society of Chemistry has an exclusive publication licence for this journal copyright_licence: This article is freely available. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (CC BY 3.0) history: Received 26 November 2015; Accepted 18 January 2016; Accepted Manuscript published 18 January 2016; Advance Article published 26 January 2016; Version of Record published 1 March 2016 ispartof: Dalton Transactions vol:45 issue:10 pages:4401-4406 ispartof: location:England status: published

Ferroelectric metal–organic frameworks are emerging as an exciting field of research and have witnessed great progress in the last decade. In this contribution, we briefly discuss ferroelectricity and its means of demonstration. Three mechanisms that lead to ferroelectricity are identified and critically discussed. On the basis of the shortcomings present in the literature, we present a protocol for the study of ferroelectricity in MOF compounds.

Recently, MIL-125(Ti) and NH2 -MIL-125(Ti), two titanium-based metal-organic frameworks, have attracted significant research attention in the field of photocatalysis for solar fuel generation. This work reveals that the differences between these structures are not only based on their light absorption range but also on the decay profile and topography of their excited states. In contrast to MIL-125(Ti), NH2 -MIL-125(Ti) shows markedly longer lifetimes of the charge-separated state, which improves photoconversion by the suppression of competing decay mechanisms. We used spectroelectrochemistry and ultrafast spectroscopy to demonstrate that upon photoexcitation in NH2 -MIL-125(Ti) the electron is located in the Ti-oxo clusters and the hole resides on the aminoterephthalate unit, specifically on the amino group. The results highlight the role of the amino group in NH2 -MIL-125(Ti), the electron donation of which extends the lifetime of the photoexcited state substantially.

Interpenetration, the entwining of multiple lattices, is a common phenomenon in metal-organic frameworks (MOFs). Typically, in interpenetrated MOFs the sub-lattices are fully occupied. Here we report a family of MOFs in which one sub-lattice is fully occupied and the occupancy level of the other can be controlled during synthesis to produce frameworks with variable levels of partial interpenetration. We also report an 'autocatenation' process, a transformation of non-interpenetrated lattices into doubly interpenetrated frameworks via progressively higher degrees of interpenetration that involves no external reagents. Autocatenation maintains crystallinity and can be triggered either thermally or by shear forces. The ligand used to construct these MOFs is chiral, and both racemic and enantiopure partially interpenetrated frameworks can be accessed. X-ray diffraction, nonlinear optical microscopy and theoretical calculations offer insights into the structures and dynamic behaviour of these materials and the growth mechanisms of interpenetrated MOFs. ispartof: Nature Chemistry vol:8 issue:3 pages:250-257 ispartof: location:England status: published

Chemistry of materials 25, 17-26 (2013). doi:10.1021/cm3025445, Published by American Chemical Society, Washington, DC

The porous MIL-47 material shows a selective adsorption behavior for para-, ortho-, and meta-isomers of xylenes, making the material a serious candidate for separation applications. The origin of the selectivity lies in the differences in interactions (energetic) and confining (entropic). This paper investigates the xylene-framework interactions and the xylene-xylene interactions with quantum mechanical calculations, using a dispersion-corrected density functional and periodic boundary conditions to describe the crystal. First, the strength and geometrical characteristics of the optimal xylene-xylene interactions are quantified by studying the pure and mixed pairs in gas phase. An extended set of initial structures is created and optimized to sample as many relative orientations and distances as possible. Next, the pairs are brought in the pores of MIL-47. The interaction with the terephthalic linkers and other xylenes increases the stacking energy in gas phase (-31.7 kJ/mol per pair) by roughly a factor four in the fully loaded state (-58.3 kJ/mol per xylene). Our decomposition of the adsorption energy shows various trends in the contributing xylene-xylene interactions. The absence of a significant difference in energetics between the isomers indicates that entropic effects must be mainly responsible for the separation behavior.