Self-assembly of a layered two-dimensional molecularly woven fabric.

Fabrics-materials consisting of layers of woven fibres-are some of the most important materials in everyday life1. Previous nanoscale weaves2-16 include isotropic crystalline covalent organic frameworks12-14 that feature rigid helical strands interlaced in all three dimensions, rather than the two-dimensional17,18 layers of flexible woven strands that give conventional textiles their characteristic flexibility, thinness, anisotropic strength and porosity. A supramolecular two-dimensional kagome weave15 and a single-layer, surface-supported, interwoven two-dimensional polymer16 have also been reported. The direct, bottom-up assembly of molecular building blocks into linear organic polymer chains woven in two dimensions has been proposed on a number of occasions19-23, but has not previously been achieved. Here we demonstrate that by using an anion and metal ion template, woven molecular 'tiles' can be tessellated into a material consisting of alternating aliphatic and aromatic segmented polymer strands, interwoven within discrete layers. Connections between slowly precipitating pre-woven grids, followed by the removal of the ion template, result in a wholly organic molecular material that forms as stacks and clusters of thin sheets-each sheet up to hundreds of micrometres long and wide but only about four nanometres thick-in which warp and weft single-chain polymer strands remain associated through periodic mechanical entanglements within each sheet. Atomic force microscopy and scanning electron microscopy show clusters and, occasionally, isolated individual sheets that, following demetallation, have slid apart from others with which they were stacked during the tessellation and polymerization process. The layered two-dimensional molecularly woven material has long-range order, is birefringent, is twice as stiff as the constituent linear polymer, and delaminates and tears along well-defined lines in the manner of a macroscopic textile. When incorporated into a polymer-supported membrane, it acts as a net, slowing the passage of large ions while letting smaller ions through.

Chemical control of structure and guest uptake by a conformationally mobile porous material.

Metal-organic frameworks (MOFs) are crystalline synthetic porous materials formed by binding organic linkers to metal nodes: they can be either rigid1,2 or flexible3. Zeolites and rigid MOFs have widespread applications in sorption, separation and catalysis that arise from their ability to control the arrangement and chemistry of guest molecules in their pores via the shape and functionality of their internal surface, defined by their chemistry and structure4,5. Their structures correspond to an energy landscape with a single, albeit highly functional, energy minimum. By contrast, proteins function by navigating between multiple metastable structures using bond rotations of the polypeptide6,7, where each structure lies in one of the minima of a conformational energy landscape and can be selected according to the chemistry of the molecules that interact with the protein. These structural changes are realized through the mechanisms of conformational selection (where a higher-energy minimum characteristic of the protein is stabilized by small-molecule binding) and induced fit (where a small molecule imposes a structure on the protein that is not a minimum in the absence of that molecule)8. Here we show that rotation about covalent bonds in a peptide linker can change a flexible MOF to afford nine distinct crystal structures, revealing a conformational energy landscape that is characterized by multiple structural minima. The uptake of small-molecule guests by the MOF can be chemically triggered by inducing peptide conformational change. This change transforms the material from a minimum on the landscape that is inactive for guest sorption to an active one. Chemical control of the conformation of a flexible organic linker offers a route to modifying the pore geometry and internal surface chemistry and thus the function of open-framework materials.

Folding a Molecular Strand into a Trefoil Knot of Single Handedness with Co(II)/Co(III) Chaperones.

We report the synthesis of a right-handed (Δ-stereochemistry of strand crossings) trefoil knot from a single molecular strand containing three pyrazine-2,5-dicarboxamide units adjacent to point-chiral centers and six pyridine moieties. The oligomeric ligand strand folds into an overhand (open-trefoil) knot through the assistance of coordinatively dynamic Co(II) "chaperones" that drive the formation of a three-metal-ion circular helicate. The entangled structure is kinetically locked by oxidation to Co(III) and covalently captured by ring-closing olefin metathesis to generate a trefoil knot of single topological handedness. The stereochemistry of the strand crossings in the metal-coordinated overhand knot is governed by the stereochemistry of the point-chiral carbon centers in the ligand strand. The overhand and trefoil knots were characterized by NMR spectroscopy, mass spectrometry, and X-ray crystallography. Removal of the metal ions from the knot, followed by hydrogenation of the alkene, yielded the wholly organic trefoil knot. The metal-free knot and parent ligand were investigated by circular dichroism (CD) spectroscopy. The CD spectra indicate that the topological stereochemistry of the knot has a greater effect on the asymmetry of the chromophore environment than do the point-chiral centers of the strand.

Isolation of a Bent Dysprosium Bis(amide) Single-Molecule Magnet.

The isolation of formally two-coordinate lanthanide (Ln) complexes is synthetically challenging, due to predominantly ionic Ln bonding regimes favoring high coordination numbers. In 2015, it was predicted that a near-linear dysprosium bis(amide) cation [Dy{N(SiiPr3)2}2]+ could provide a single-molecule magnet (SMM) with an energy barrier to magnetic reversal (Ueff) of up to 2600 K, a 3-fold increase of the record Ueff for a Dy SMM at the time; this work showed a potential route to SMMs that can provide high-density data storage at higher temperatures. However, synthetic routes to a Dy complex containing only two monodentate ligands have not previously been realized. Here, we report the synthesis of the target bent dysprosium bis(amide) complex, [Dy{N(SiiPr3)2}2][Al{OC(CF3)3}4] (1-Dy), together with the diamagnetic yttrium analogue. We find Ueff = 950 ± 30 K for 1-Dy, which is much lower than the predicted values for idealized linear two-coordinate Dy(III) cations. Ab initio calculations of the static electronic structure disagree with the experimentally determined height of the Ueff barrier, thus magnetic relaxation is faster than expected based on magnetic anisotropy alone. We propose that this is due to enhanced spin-phonon coupling arising from the flexibility of the Dy coordination sphere, in accord with ligand vibrations being of equal importance to magnetic anisotropy in the design of high-temperature SMMs.

N-Heterocyclic Carbene to Actinide d-Based π-bonding Correlates with Observed Metal-Carbene Bond Length Shortening Versus Lanthanide Congeners.

Comparison of bonding and electronic structural features between trivalent lanthanide (Ln) and actinide (An) complexes across homologous series' of molecules can provide insights into subtle and overt periodic trends. Of keen interest and debate is the extent to which the valence f- and d-orbitals of trivalent Ln/An ions engage in covalent interactions with different ligand donor functionalities and, crucially, how bonding differences change as both the Ln and An series are traversed. Synthesis and characterization (SC-XRD, NMR, UV-vis-NIR, and computational modeling) of the homologous lanthanide and actinide N-heterocyclic carbene (NHC) complexes [M(C5Me5)2(X)(IMe4)] {X = I, M = La, Ce, Pr, Nd, U, Np, Pu; X = Cl, M = Nd; X = I/Cl, M = Nd, Am; and IMe4 = [C(NMeCMe)2]} reveals consistently shorter An-C vs Ln-C distances that do not substantially converge upon reaching Am3+/Nd3+ comparison. Specifically, the difference of 0.064(6) Å observed in the La/U pair is comparable to the 0.062(4) Å difference observed in the Nd/Am pair. Computational analyses suggest that the cause of this unusual observation is rooted in the presence of π-bonding with the valence d-orbital manifold in actinide complexes that is not present in the lanthanide congeners. This is in contrast to other documented cases of shorter An-ligand vs Ln-ligand distances, which are often attributed to increased 5f vs 4f radial diffusivity leading to differences in 4f and 5f orbital bonding involvement. Moreover, in these traditional observations, as the 5f series is traversed, the 5f manifold contracts such that by americium structural studies often find no statistically significant Am3+vs Nd3+ metal-ligand bond length differences.

Studying Cation Exchange in {Cr7Co} Pseudorotaxanes: Preparatory Studies for Making Hybrid Molecular Machines.

In the design of dynamic supramolecular systems used in molecular machines, it is important to understand the binding preferences between the macrocycle and stations along the thread. Here, we apply 1H NMR spectroscopy to investigate the relative stabilities of a series of linear alkylammonium templated pseudorotaxanes with the general formula [H2NRR'][Cr7CoF8(O2CCH2 tBu)16] by exchanging the cation in solution. Our results show that the pseudorotaxanes are able to exchange threads via a dissociative mechanism. The position of equilibrium is dependent upon the ammonium cation and solvent used. Short chain primary ammonium cations are shown to be far less favourable macrocycle stations than secondary ammonium cations. Collision-induced dissociation mass spectrometry (CID-MS) has been used to look at disassembly of the pseudorotaxanes in a solvent-free environment and stability trends compared to those in acetone-d6. The energy needed to induce 50 % of the precursor ion loss (E50) is used and shows a similar trend to the equilibria measured by NMR. The relative stabilities of these hybrid inorganic-organic pseudo-rotaxanes are different to those of host-guest compounds involving crown ethers and this may be valuable for the design of molecular machines.

Zintl Clusters as a Platform for Lewis Acid Catalysis.

Clusters of the main group elements phosphorus and arsenic, commonly categorized as Zintl clusters, have been known for over a century. And, only now is the application of these systems as catalysts for organic synthesis being investigated. In this work, boranes are tethered via an aliphatic linker to Zintl-based clusters and their Lewis acidity is examined experimentally, by the Gutmann-Beckett test and competency in the hydroborative reduction of six organic substrates, as well as computationally, by fluoride ion affinity and hydride ion affinity methods. The effects of tuning the aliphatic linker length, substituents at the boron, and changing the cluster from a seven-atom phosphorus system to a seven-atom arsenic system on reactivity are studied.

Halobenzene Adducts of a Dysprosocenium Single-Molecule Magnet.

Dysprosium complexes with strong axial crystal fields are promising candidates for single-molecule magnets (SMMs), which could be used for high-density data storage. Isolated dysprosocenium cations, [Dy(CpR)2]+ (CpR = substituted cyclopentadienyl), have recently shown magnetic hysteresis (a memory effect) above the temperature of liquid nitrogen. Synthetic efforts have focused on reducing strong transverse ligand fields in these systems as they are known to enhance magnetic relaxation by spin-phonon mechanisms. Here we show that equatorial coordination of the halobenzenes PhX (X = F, Cl, Br) and o-C6H4F2 to the cation of a recently reported dysprosocenium complex [Dy(Cpttt)(Cp*)][Al{OC(CF3)3}4] (Cpttt = C5H2tBu3-1,2,4; Cp* = C5Me5) reduces magnetic hysteresis temperatures compared to that of the parent cation. We find that this is due to increased effectiveness of both one- (Orbach) and two-phonon (Raman) relaxation mechanisms, which correlate with the electronegativity and number of interactions with the halide despite κ1-coordination of a single halobenzene having a minimal effect on the metrical parameters of [Dy(Cpttt)(Cp*)(PhX-κ1-X)]+ cations vs the isolated [Dy(Cpttt)(Cp*)]+ cation. We observe unusual divergent behavior of relaxation rates at low temperatures in [Dy(Cpttt)(Cp*)(PhX)][Al{OC(CF3)3}4], which we attribute to a phonon bottleneck effect. We find that, despite the transverse fields introduced by the monohalobenzenes in these cations, the interactions are sufficiently weak that the effective barriers to magnetization reversal remain above 1000 cm-1, being only ca. 100 cm-1 lower than for the parent complex, [Dy(Cpttt)(Cp*)][Al{OC(CF3)3}4].

Synthesis and Magnetic Properties of Bis-Halobenzene Decamethyldysprosocenium Cations.

The decamethyldysprosocenium cation, [Dy(Cp*)2]+ (Cp* = {C5Me5}), was a target single-molecule magnet (SMM) prior to the isolation of larger dysprosocenium cations, which have recently shown magnetic memory effects up to 80 K. However, the relatively short Dy···Cp*centroid distances of [Dy(Cp*)2]+, together with the reduced resonance of its vibrational modes with electronic states compared to larger dysprosocenium cations, could lead to more favorable SMM behavior. Here, we report the synthesis and magnetic properties of a series of solvated adducts containing bis-halobenzene decamethyldysprosocenium cations, namely [Dy(Cp*)2(PhX-κ-X)2][Al{OC(CF3)3}4] (X = F or Cl) and [Dy(Cp*)2(C6H4F2-κ2-F,F)(C6H4F2-κ-F)][Al{OC(CF3)3}4]. These complexes were prepared by the sequential reaction of [Dy(Cp*)2(µ-BH4)]∞ with allylmagnesium chloride and [NEt3H][Al{OC(CF3)3}4], followed by recrystallization from parent halobenzenes. The complexes were characterized by powder and single crystal X-ray diffraction, NMR and ATR-IR spectroscopy, elemental analysis, and SQUID magnetometry; experimental data were rationalized by a combination of density functional theory and ab initio calculations. We find that bis-halobenzene adducts of the [Dy(Cp*)2]+ cation exhibit highly bent Cp*···Dy···Cp* angles; these cations are also susceptible to decomposition by C-X (X = F, Cl, Br) activation and displacement of halobenzenes by O-donor ligands. The effective energy barrier to reversal of magnetization measured for [Dy(Cp*)2(PhF-κ-F)2][Al{OC(CF3)3}4] (930(6) cm-1) sets a new record for SMMs containing {Dy(Cp*)2} fragments, though all SMM parameters are lower than would be predicted for an isolated [Dy(Cp*)2]+ cation, as expected due to transverse ligand fields introduced by halobenzenes and the large deviation of the Cp*···Dy···Cp* angle from linearity promoting magnetic relaxation.

Amino Functionality Enables Aqueous Synthesis of Carboxylic Acid-Based MOFs at Room Temperature by Biomimetic Crystallization.

Enzyme immobilization within metal-organic frameworks (MOFs) is a promising solution to avoid denaturation and thereby utilize the desirable properties of enzymes outside of their native environments. The biomimetic mineralization strategy employs biomacromolecules as nucleation agents to promote the crystallization of MOFs in water at room temperature, thus overcoming pore size limitations presented by traditional postassembly encapsulation. Most biomimetic crystallization studies reported to date have employed zeolitic imidazole frameworks (ZIFs). Herein, we expand the library of MOFs suitable for biomimetic mineralization to include zinc(II) MOFs incorporating functionalized terephthalic acid linkers and study the catalytic performance of the enzyme@MOFs. Amine functionalization of terephthalic acids is shown to accelerate the formation of crystalline MOFs enabling new enzyme@MOFs to be synthesized. The structure and morphology of the enzyme@MOFs were characterized by PXRD, FTIR, and SEM-EDX, and the catalytic potential was evaluated. Increasing the linker length while retaining the amino moiety gave rise to a family of linkers; however, MOFs generated with the 2,2'-aminoterephthalic acid linker displayed the best catalytic performance. Our data also illustrate that the pH of the reaction mixture affects the crystal structure of the MOF and that this structural transformation impacts the catalytic performance of the enzyme@MOF.

Weak Exchange Interactions in Multispin Systems: EPR Studies of Metalloporphyrins Decorated with {Cr7Ni} Rings.

Both metalloporphyrins and heterometallic {Cr7Ni} rings are of significant research interest due to their proposed roles in quantum information processing devices. In this study, we present a series of complexes in which [Cr7NiF3(Etglu)(O2CtBu)15] (N-EtgluH5 = N-ethyl-d-glucamine) heterometallic rings are coordinated to metalloporphyrin linkers: the symmetric [M(TPyP)] for M = Cu2+, VO2+, and H2TPyP = 5,10,15,20-tetra(4-pyridyl)porphyrin; and the asymmetric [{VO}(TrPPyP)] for H2(TrPPyP) = 5,10,15-(triphenyl)-20-(4-pyridyl)porphyrin. The magnetic interactions present in these complexes are unraveled using the continuous wave (CW) electron paramagnetic resonance (EPR) technique. The nature of the coupling between the {Cr7Ni} rings and the central metalloporphyrin is assessed by numerical simulations of CW EPR spectra and determined to be on the order of 0.01 cm-1, larger than the dipolar ones and suitable for individual spin addressability in multiqubit architectures.

AtomAccess: A Predictive Tool for Molecular Design and Its Application to the Targeted Synthesis of Dysprosium Single-Molecule Magnets.

Isolated dysprosocenium cations, [Dy(CpR)2]+ (CpR = substituted cyclopentadienyl), have recently been shown to exhibit superior single-molecule magnet (SMM) properties over closely related complexes with equatorially bound ligands. However, gauging the crossover point at which the CpR substituents are large enough to prevent equatorial ligand binding, but small enough to approach the metal closely and generate strong crystal field splitting has required laborious synthetic optimization. We therefore created the computer program AtomAccess to predict the accessibility of a metal binding site and its ability to accommodate additional ligands. Here, we apply AtomAccess to identify the crossover point for equatorial coordination in [Dy(CpR)2]+ cations in silico and hence predict a cation that is at the cusp of stability without equatorial interactions, viz., [Dy(Cpttt)(Cp*)]+ (Cpttt = C5H2tBu3-1,2,4, Cp* = C5Me5). Upon synthesizing this cation, we found that it crystallizes as either a contact ion-pair, [Dy(Cpttt)(Cp*){Al[OC(CF3)3]4-κ-F}], or separated ion-pair polymorph, [Dy(Cpttt)(Cp*)][Al{OC(CF3)3}4]·C6H6. Upon characterizing these complexes, together with their precursors, yttrium and yttrium-doped analogues, we find that the contact ion-pair shows inferior SMM properties to the separated ion-pair, as expected, due to faster Raman and quantum tunneling of magnetization relaxation processes, while the Orbach region is relatively unaffected. The experimental verification of the predicted crossover point for equatorial coordination in this work tests the limitations of the use of AtomAccess as a predictive tool and also indicates that the application of this type of program shows considerable potential to boost efficiency in exploratory synthetic chemistry.

Control and Transferability of Magnetic Interactions in Supramolecular Structures: Trimers of {Cr7 Ni} Antiferromagnetic Rings.

A synthetic strategy is demonstrated to prepare two distinct trimers of antiferromagnetically coupled {Cr7 Ni} rings, substantially varying the magnetic interactions between the spin centres. The interactions were studied using multi-frequency cw EPR: in a trimer linked via non-covalent H-bonding interactions no measurable interaction between rings was seen, while in a trimer linked via iso-nicotinate groups isotropic and anisotropic exchange interactions of +0.42 and -0.8 GHz, respectively, were observed. The latter are the same as those for a simpler hetero-dimer system, showing how the spin-spin interactions can be built in a predictable and modular manner in these systems.

Breathing Behaviour Modification of Gallium MIL-53 Metal-Organic Frameworks Induced by the Bridging Framework Inorganic Anion.

Controlling aspects of the µ2 -X- bridging anion in the metal-organic framework Ga-MIL-53 [GaX(bdc)] (X- =(OH)- or F- , bdc=1, 4-benzenedicarboxylate) is shown to direct the temperature at which thermally induced breathing transitions of this framework occur. In situ single crystal X-ray diffraction studies reveal that substituting 20 % of (OH)- in [Ga(OH)(bdc)] (1) for F- to produce [Ga(OH)0.8 F0.2 (bdc)] (2) stabilises the large pore (lp) form relative to the narrow pore (np) form, causing a well-defined decrease in the onset of the lp to np transition at higher temperatures, and the adsorption/desorption of nitrogen at lower temperatures through np to lp to intermediate (int) pore transitions. These in situ diffraction studies have also yielded a more plausible crystal structure of the int-[GaX(bdc)] ⋅ H2 O phases and shown that increasing the heating rate to a flash heating regime can enable the int-[GaX(bdc)] ⋅ H2 O to lp-[GaX(bdc)] transition to occur at a lower temperature than np-[GaX(bdc)] via an unreported pathway.

Chemically Fueled Communication Along a Scaffolded Nanoscale Array of Squaramides.

Relaying conformational change over several nanometers is central to the function of allosterically regulated proteins. Replicating this mechanism artificially would provide important communication tools, but requires nanometer-sized molecules that reversibly switch between defined shapes in response to signaling molecules. In this work, 1.8 nm long rigid rod oligo(phenylene-ethynylene)s are scaffolds for switchable multi-squaramide hydrogen-bond relays. Each relay can adopt either a parallel or an antiparallel orientation relative to the scaffold; the preferred orientation is dictated by a director group at one end. An amine director responded to proton signals, with acid-base cycles producing multiple reversible changes in relay orientation that were reported by a terminal NH, which is 1.8 nm distant. Moreover, a chemical fuel acted as a dissipative signal. As the fuel was consumed, the relay reverted to its original orientation, illustrating how information from out-of-equilibrium molecular signals can be communicated to a distant site.

Organic thermally activated delayed fluorescence material with strained benzoguanidine donor.

Organic thermally activated delayed fluorescence (TADF) materials have been widely investigated due to their impressive electronic properties and applied potential for the third generation of organic light-emitting diodes (OLED). We present organic TADF material (4BGIPN) based on the strained benzoguanidine donor and compare it with the benchmark carbazole-based material (4CzIPN). Extended π-conjugation in 4BGIPN material results in yellow-green luminescence at 512 nm with a fast radiative rate of 5.5 × 10-5 s-1 and a photoluminescence quantum yield of 46% in methylcyclohexane solution. Such a nitrogen-rich 4BGIPN material has a significantly stabilized highest occupied molecular orbital (HOMO) at -6.4 eV while the lowest unoccupied molecular orbital (LUMO) at -4.0 eV, indicating potential suitability for application as the electron transport layer or TADF class III emitter in OLEDs.

A Chiral 19F NMR Reporter of Foldamer Conformation in Bilayers.

Understanding and controlling peptide foldamer conformation in phospholipid bilayers is a key step toward their use as molecular information relays in membranes. To this end, a new 19F "reporter" tag has been developed and attached to dynamic peptide foldamers. The (R)-1-(trifluoromethyl)ethylamido ((R)-TFEA) reporter was attached to the C-terminus of α-amino-iso-butyric acid (Aib) foldamers. Crystallography confirmed that the foldamers adopted 310 helical conformations. Variable temperature (VT) NMR spectroscopy in organic solvents showed that the (R)-TFEA reporter had an intrinsic preference for P helicity, but the overall screw-sense was dominated by a chiral "controller" at the N-terminus. The 19F NMR chemical shift of the CF3 resonance was correlated with the ability of different N-terminal groups to induce either an M or a P helix in solution. In bilayers, a similar correlation was found. Solution 19F NMR spectroscopy on small unilamellar vesicle (SUV) suspensions containing the same family of (R)-TFEA-labeled foldamers showed broadened but resolvable 19F resonances, with each chemical shift mirroring their relative positions in organic solvents. These studies showed that foldamer conformational preferences are the same in phospholipid bilayers as in organic solvents and also revealed that phospholipid chirality has little influence on conformation.

A Zintl Cluster for Transition Metal-Free Catalysis: C═O Bond Reductions.

The first fully characterized boron-functionalized heptaphosphide Zintl cluster, [(BBN)P7]2- ([1]2-), is synthesized by dehydrocoupling [HP7]2-. Dehydrocoupling is a previously unprecedented reaction pathway to functionalize Zintl clusters. [Na(18-c-6)]2[1] was employed as a transition metal-free catalyst for the hydroboration of aldehydes and ketones. Moreover, the greenhouse gas carbon dioxide (CO2) was efficiently and selectively reduced to methoxyborane. This work represents the first examples of Zintl catalysis where the transformation is transition metal-free and where the cluster is noninnocent.

Five-Spin Supramolecule for Simulating Quantum Decoherence of Bell States.

We report a supramolecule that contains five spins of two different types and with, crucially, two different and predictable interaction energies between the spins. The supramolecule is characterized, and the interaction energies are demonstrated by electron paramagnetic resonance (EPR) spectroscopy. Based on the measured parameters, we propose experiments that would allow this designed supramolecule to be used to simulate quantum decoherence in maximally entangled Bell states that could be used in quantum teleportation.

Disassembly Mechanisms and Energetics of Polymetallic Rings and Rotaxanes.

Understanding the fundamental reactivity of polymetallic complexes is challenging due to the complexity of their structures with many possible bond breaking and forming processes. Here, we apply ion mobility mass spectrometry coupled with density functional theory to investigate the disassembly mechanisms and energetics of a family of heterometallic rings and rotaxanes with the general formula [NH2RR'][Cr7MF8(O2CtBu)16] with M = MnII, FeII, CoII, NiII, CuII, ZnII, CdII. Our results show that their stability can be tuned both by altering the d-metal composition in the macrocycle and by the end groups of the secondary ammonium cation [NH2RR']+. Ion mobility probes the conformational landscape of the disassembly process from intact complex to structurally distinct isobaric fragments, providing unique insights to how a given divalent metal tunes the structural dynamics.