Novel semiconducting iron–quinizarin metal–organic framework for application in supercapacitors^*

We present conductivity data for a newly synthesised metal organic framework FeQ, Fe(C14H6O4).H2O demonstrating significant electronic transport. The electrical conductivity of the material is expected to be through the π-π interaction of the ligand- quinizarin and is measured to be 1.73 × 10-2 Scm-1. Its potential role as supercapacitor electrodes is discussed

Conformational Flexibility of Hybrid [3]- and [4]-Rotaxanes

The synthesis, structures, and properties of [4]- and [3]-rotaxane complexes are reported where [2]-rotaxanes, formed from heterometallic {Cr7Ni} rings, are bound to a fluoride-centered {CrNi2} triangle. The compounds have been characterized by single-crystal X-ray diffraction and have the formulas [CrNi2(F)(O2CtBu)6]{(BH)[Cr7NiF8(O2CtBu)16]}3 (3) and [CrNi2(F)(O2CtBu)6(THF)]{(BH)[Cr7NiF8(O2CtBu)16]}2 (4), where B = py-CH2CH2NHCH2C6H4SCH3. The [4]-rotaxane 3 is an isosceles triangle of three [2]-rotaxanes bound to the central triangle while the [3]-rotaxane 4 contains only two [2]-rotaxanes bound to the central triangle. Studies of the behavior of 3 and 4 in solution by small-angle X-ray scattering and atomistic molecular dynamic simulations show that the structure of 3 is similar to that found in the crystal but that 4 has a different conformation to the crystal. Continuous wave and pulsed electron paramagnetic resonance spectroscopy was used to study the structures present and demonstrate that in frozen solutions (at 5 K) 4 forms more extended molecules than 3 and with a wider range of conformations

Breathing-Dependent Redox Activity in a Tetrathiafulvalene-Based Metal-Organic Framework

“Breathing” metal–organic frameworks (MOFs) that involve changes in their structural and physical properties upon an external stimulus are an interesting class of crystalline materials due to their range of potential applications including chemical sensors. The addition of redox activity opens up a new pathway for multifunctional “breathing” frameworks. Herein, we report the continuous breathing behavior of a tetrathiafulvalene (TTF)-based MOF, namely MUV-2, showing a reversible swelling (up to ca. 40% of the volume cell) upon solvent adsorption. Importantly, the planarity of the TTF linkers is influenced by the breathing behavior of the MOF, directly impacting on its electrochemical properties and thus opening the way for the development of new electrochemical sensors. Quantum chemical calculations and Raman spectroscopy have been used to provide insights into the tunability of the oxidation potential

Braiding a molecular knot with eight crossings

Knots may ultimately prove just as versatile and useful at the nanoscale as at the macroscale. However, the lack of synthetic routes to all but the simplest molecular knots currently prevents systematic investigation of the influence of knotting at the molecular level.We found that it is possible to assemble four building blocks into three braided ligand strands. Octahedral iron(II) ions control the relative positions of the three strands at each crossing point in a circular triple helicate, while structural constraints on the ligands determine the braiding connections. This approach enables two-step assembly of a molecular 8 19 knot featuring eight nonalternating crossings in a 192-atom closed loop ~20 nanometers in length. The resolved metal-free 8 19 knot enantiomers have pronounced features in their circular dichroism spectra resulting solely from topological chirality

Allosteric initiation and regulation of catalysis with a molecular knot

Molecular knots occur in DNA, proteins, and other macromolecules. However, the benefits that can potentially arise from tying molecules in knots are, for the most part, unclear. Here, we report on a synthetic molecular pentafoil knot that allosterically initiates or regulates catalyzed chemical reactions by controlling the in situ generation of a carbocation formed through the knot-promoted cleavage of a carbon-halogen bond. The knot architecture is crucial to this function because it restricts the conformations that the molecular chain can adopt and prevents the formation of catalytically inactive species upon metal ion binding. Unknotted analogs are not catalytically active. Our results suggest that knotting molecules may be a useful strategy for reducing the degrees of freedom of flexible chains, enabling them to adopt what are otherwise thermodynamically inaccessible functional conformations

Quantum spin coherence in halogen-modified Cr7Ni molecular nanomagnets

Among the factors determining the quantum coherence of the spin in molecular magnets are the presence and the nature of nuclear spins in the molecule. We have explored modifying the nuclear-spin environment in Cr7Ni-based molecular nanomagnets by replacing hydrogen atoms with deuterium or the halogen atoms, fluorine or chlorine. We find that the spin coherence, studied at low temperatures by pulsed electron-spin resonance, is modified by a range of factors, including nuclear spin and magnetic moment, changes in dynamics owing to nuclear mass, and molecular morphology changes

Allosteric initiation and regulation of catalysis with a molecular knot

Molecular knots occur in DNA, proteins, and other macromolecules. However, the benefits that can potentially arise from tying molecules in knots are, for the most part, unclear. Here, we report on a synthetic molecular pentafoil knot that allosterically initiates or regulates catalyzed chemical reactions by controlling the in situ generation of a carbocation formed through the knot-promoted cleavage of a carbon-halogen bond. The knot architecture is crucial to this function because it restricts the conformations that the molecular chain can adopt and prevents the formation of catalytically inactive species upon metal ion binding. Unknotted analogs are not catalytically active. Our results suggest that knotting molecules may be a useful strategy for reducing the degrees of freedom of flexible chains, enabling them to adopt what are otherwise thermodynamically inaccessible functional conformations