Using Catalysis to Drive Chemistry Away from Equilibrium: Relating Kinetic Asymmetry, Power Strokes, and the Curtin-Hammett Principle in Brownian Ratchets.

Chemically fueled autonomous molecular machines are catalysis-driven systems governed by Brownian information ratchet mechanisms. One fundamental principle behind their operation is kinetic asymmetry, which quantifies the directionality of molecular motors. However, it is difficult for synthetic chemists to apply this concept to molecular design because kinetic asymmetry is usually introduced in abstract mathematical terms involving experimentally inaccessible parameters.

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We report the synthesis of molecular prime and composite knots by social self-sorting of 2,6-pyridinedicarboxamide (pdc) ligands of differing topicity and stereochemistry. Upon mixing achiral monotopic and ditopic pdc-ligand strands in a 1:1:1 ratio with Lu(III), a well-defined heteromeric complex featuring one of each ligand strand and the metal ion is selectively formed. Introducing point-chiral centers into the ligands leads to single-sense helical stereochemistry of the resulting coordination complex.

Autonomous fuelled directional rotation about a covalent single bond.

Biology operates through autonomous chemically fuelled molecular machinery, including rotary motors such as adenosine triphosphate synthase and the bacterial flagellar motor. Chemists have long sought to create analogous molecular structures with chemically powered, directionally rotating, components. However, synthetic motor molecules capable of autonomous 360° directional rotation about a single bond have proved elusive, with previous designs lacking either autonomous fuelling or directionality.

Insights from an information thermodynamics analysis of a synthetic molecular motor.

Information is physical, a realization that has transformed the physics of measurement and communication. However, the flow between information, energy and mechanics in chemical systems remains largely unexplored. Here we analyse a minimalist autonomous chemically driven molecular motor in terms of information thermodynamics, a framework that quantitatively relates information to other thermodynamic parameters.

Vernier template synthesis of molecular knots.

Molecular knots are often prepared using metal helicates to cross the strands. We found that coordinatively mismatching oligodentate ligands and metal ions provides a more effective way to synthesize larger knots using Vernier templating. Strands composed of different numbers of tridentate 2,6-pyridinedicarboxamide groups fold around nine-coordinate lanthanide (III) ions to generate strand-entangled complexes with the lowest common multiple of coordination sites for the ligand strands and metal ions.

Direct solid-phase synthesis of molecular heterooligonuclear lanthanoid-complexes.

Molecular lanthanoid complexes are highly valuable building blocks for a number of important technological applications, e.g. as contrast agents in magnetic resonance imaging (MRI) or as luminescent probes for bioassays.

Circularly Polarised Luminescence in Enantiopure Samarium and Europium Cryptates.

Circularly polarised luminescence (CPL) is a chiroptical phenomenon gaining more and more attention, as the availability of the necessary spectrometers is getting better and first applications in bioimaging or for the preparation of OLEDs (organic light emitting diodes) are coming within range. Until now most examples of distinctly CPL-active compounds were europium and terbium complexes though theoretically the electronic structure of samarium should be as suitable as the one of terbium. This discrepancy can be accounted for by the high susceptibility of samarium to non-radiative deactivation processes.

Deuterated Molecular Ruby with Record Luminescence Quantum Yield.

The recently reported luminescent chromium(III) complex 1 ([Cr(ddpd) ] ; ddpd=N,N'-dimethyl-N,N'-dipyridine-2-yl-pyridine-2,6-diamine) shows exceptionally strong near-IR emission at 775 nm in water under ambient conditions (Φ=11 %) with a microsecond lifetime as the ligand design in 1 effectively eliminates non-radiative decay pathways, such as photosubstitution, back-intersystem crossing, and trigonal twists. In the absence of energy acceptors, such as dioxygen, the remaining decay pathways are energy transfer to high energy solvent and ligand oscillators, namely OH and CH stretching vibrations. Selective deuteration of the solvents and the ddpd ligands probes the efficiency of these oscillators in the excited state deactivation.

Chiral Resolution of Lanthanoid Cryptates with Extreme Configurational Stability.

Chiral resolution is achieved for racemic tris(2,2'-bipyridine)-based lanthanoid cryptates by chiral HPLC. The resolved complexes exhibit very rare configurational stability under extreme conditions.

Magnetic Anisotropy in Functionalized Bipyridyl Cryptates.

The magnetic properties of molecular lanthanoid complexes are very important for a variety of scientific and technological applications, with the unique magnetic anisotropy being one of the most important features. In this context, a very rigid tris(bipyridine) cryptand was synthesized with a primary amine functionality for future bioconjugation. The magnetic anisotropy was investigated for the corresponding paramagnetic ytterbium cryptate.

Breakdown of the energy gap law in molecular lanthanoid luminescence: the smallest energy gap is not universally relevant for nonradiative deactivation.

For several decades, the energy gap law has been the prevalent theoretical framework for the discussion of nonradiative deactivation of lanthanoid luminescence in molecular coordination chemistry. Here we show experimentally on samarium and dysprosium model complexes that the size of the energy gap ΔE between a lanthanoid emitting state and the next-lower electronic state cannot be considered a reliable and accurate predictor of the quantitative extent of nonradiative deactivation by aromatic C-H and C-D oscillator overtones. Because the energy gap is the central pillar for the entire conceptual framework of the energy gap law, this finding amounts to largely invalidating this theory for the quantitative description of molecular multiphonon relaxation.