Switched "On" Transient Fluorescence Output from a Pulsed-Fuel Molecular Ratchet.

We report the synthesis and operation of a molecular energy ratchet that transports a crown ether from solution onto a thread, along the axle, over a fluorophore, and off the other end of the thread back into bulk solution, all in response to a single pulse of a chemical fuel (CCl3CO2H). The fluorophore is a pyrene residue whose fluorescence is normally prevented by photoinduced electron transfer (PET) to a nearby N-methyltriazolium group. However, crown ether binding to the N-methyltriazolium site inhibits the PET, switching on pyrene fluorescence under UV irradiation. Each pulse of fuel results in a single ratchet cycle of transient fluorescence (encompassing threading, transport to the N-methyltriazolium site, and then dethreading), with the onset of the fluorescent time period determined by the amount of fuel in each pulse and the end-point determined by the concentration of the reagents for the disulfide exchange reaction. The system provides a potential alternative signaling approach for artificial molecular machines that read symbols from sequence-encoded molecular tapes.

Structure and Properties of a Five-Coordinate Nickel(II) Porphyrin.

Axial coordination in nickel(II) porphyrins has been thoroughly investigated and is well understood. However, isolated five-coordinate nickel(II) porphyrins are still elusive after 50 years of intense research, even though they play a crucial role as intermediates in enzymes and catalysts. Herein we present the first fully stable, thoroughly characterized five-coordinate nickel(II) porphyrin in solution and in the solid state (crystal structure). The spectroscopic properties indicate pure high-spin behavior (S = 1). There are distinct differences in the NMR, UV-vis, and redox behavior compared to those of high-spin six-coordinate [with two axial ligands, such as NiTPPF10·(py)2] and low-spin four-coordinate (NiTPPF10) nickel(II) porphyrins. The title compound, a strapped nickel(II) porphyrin, allows a direct comparison of four-, five-, and six-coordinate nickel(II) porphyrins, depending on the environment. With this reference in hand, previous results were reevaluated, for example, the switching efficiencies and thermodynamic data of nickel(II) porphyrin-based spin switches in solution.

Dendronised Ni(ii) porphyrins as photoswitchable contrast agents for MRI.

Light-responsive contrast agents for magnetic resonance imaging (MRI) based on Ni(ii) porphyrin molecular spin switches have recently been introduced. We present their implementation in water and methanol based gels leading to the first soft materials that are rewritable with light and readable with MRI. Light of two different wavelengths as non-invasive stimuli can be applied to switch MRI contrast on and off, with a high spatiotemporal resolution and without fatigue.

Dynamic Control of Chiral Space Through Local Symmetry Breaking in a Rotaxane Organocatalyst.

We report on a switchable rotaxane molecular shuttle that features a pseudo-meso 2,5-disubstituted pyrrolidine catalytic unit on the axle whose local symmetry is broken according to the position of a threaded benzylic amide macrocycle. The macrocycle can be selectively switched (with light in one direction; with catalytic acid in the other) with high fidelity between binding sites located to either side of the pyrrolidine unit. The position of the macrocycle dictates the facial bias of the rotaxane-catalyzed conjugate addition of aldehydes to vinyl sulfones. The pseudo-meso non-interlocked thread does not afford significant selectivity as a catalyst (2-14 % ee), whereas the rotaxane affords selectivities of up to 40 % ee with switching of the position of the macrocycle changing the handedness of the product formed (up to 60 % Δee).

Speeding up NMR by in Situ Photo-Induced Reversible Acceleration of T1 -Relaxation (PIRAT).

Increasing the signal-to-noise ratio is one of the major goals in the field of NMR spectroscopy. In this proof of concept, we accelerate relaxation during an NMR pulse sequence using photo-generated paramagnetic states of an inert sensitizer. For the follow-up acquisition period, the system is converted to a diamagnetic state. The reversibility of the photo-induced switching allows extensive repetition required for multidimensional NMR. We thus eliminate the obstacle of line-broadening by the presence of paramagnetic species. In this contribution, we show how cycling of synchronized light/pulse sequences leads to an enhanced efficiency in multidimensional NMR. Our approach utilizes a molecular spin switch reversibly altering between a paramagnetic and diamagnetic state.

Photoswitchable Magnetic Resonance Imaging Contrast by Improved Light-Driven Coordination-Induced Spin State Switch.

We present a fully reversible and highly efficient on-off photoswitching of magnetic resonance imaging (MRI) contrast with green (500 nm) and violet-blue (435 nm) light. The contrast change is based on intramolecular light-driven coordination-induced spin state switch (LD-CISSS), performed with azopyridine-substituted Ni-porphyrins. The relaxation time of the solvent protons in 3 mM solutions of the azoporphyrins in DMSO was switched between 3.5 and 1.7 s. The relaxivity of the contrast agent changes by a factor of 6.7. No fatigue or side reaction was observed, even after >100,000 switching cycles in air at room temperature. Electron-donating substituents at the pyridine improve the LD-CISSS in two ways: better photostationary states are achieved, and intramolecular binding is enhanced.

Coordination-induced spin-state switching with nickel chlorin and nickel isobacteriochlorin.

We present the first coordination-induced spin-state switching with nickel chlorin and nickel isobacteriochlorin. The spin-state switching was monitored by UV-vis spectroscopy and NMR titration experiments. The association constants (K1 and K2) and thermodynamic parameters (ΔH and ΔS) of the coordination of pyridine were determined. The first X-ray analyses of a paramagnetic nickel chlorin and a nickel isobacteriochlorin provide further information about the structure of the octahedral complexes. Nickel chlorin and even more pronounced nickel isobacteriochlorin exhibit stronger coordination of axial ligands compared to the corresponding nickel porphyrin and thus provide the basis for more efficient spin-switching systems.

Photoswitching in nanoporous, crystalline solids: an experimental and theoretical study for azobenzene linkers incorporated in MOFs.

In this article, we use the popular photoswitchable molecule, azobenzene, to demonstrate that the embedding in a nanoporous, crystalline solid enables a precise understanding of light-induced, reversible molecular motion. We investigate two similar azobenzene-containing, pillared-layer metal-organic frameworks (MOFs): Cu2(AzoBPDC)2(BiPy) and Cu2(NDC)2(AzoBiPy). Experimental results from UV-vis spectroscopy and molecular uptake experiments as well as theoretical results based on density-functional theory (DFT) show that in the Cu2(AzoBPDC)2(BiPy) MOF structure, the azobenzene side groups undergo photoisomerization when irradiated with UV or visible light. In a very similar MOF structure, Cu2(NDC)2(AzoBiPy), the experimental studies show an unexpected absence of photoisomerization. The DFT calculations reveal that in both MOFs the initial and final states of the photoswitching process (the trans and the cis conformation) have similar energies, which strongly suggests that the reason for the effective blocking of photoswitching in the AzoBiPy-based MOFs must be related to the switching process itself. More detailed calculations show that in Cu2(NDC)2(AzoBiPy) a naphthalene linker from the molecular framework blocks the photoisomerization trajectory which leads from the trans to the cis conformation. For Cu2(AzoBPDC)2(BiPy), as a result of the different geometry, such a steric hindrance is absent.

Modular Synthetic Route to Monofunctionalized Porphyrin Architectures.

The synthesis of a borylated Ni2+ porphyrin and its application as a versatile precursor for building up functional ortho-substituted tetraaryl porphyrin architectures is reported. This precursor porphyrin provides the basis for efficient modular syntheses of porphyrin compounds with covalently attached axial ligands which are important as enzyme model complexes, electron transfer dyads, and many other applications. In the present study, the precursor porphyrin was used for the synthesis of molecular spin switches which previously showed high potential as photoresponsive contrast agents for magnetic resonance imaging.

Coordination-induced spin-state-switch (CISSS) in water.

We present a non-ionic water-soluble porphyrin that does not exhibit measurable aggregation even at high concentrations in water. The spin state of the corresponding nickel(II) complex changes from completely diamagnetic (low-spin) to paramagnetic (high-spin) upon addition of a strong axial ligand. This leads to a strongly reduced NMR relaxation time of the water protons even at low concentrations of the complex.

Photoswitching in two-component surface-mounted metal-organic frameworks: optically triggered release from a molecular container.

The remote control of surface properties is one of the key challenges in interfacial systems chemistry. Here, we report the realization of a SURMOF (surface-mounted metal-organic framework)-based hybrid system in which a crucial component can be switched by light. The realization of this two-component system is made possible by installing vertical compositional gradients via liquid-phase epitaxy. After loading the porous coating with guest molecules, its release is initiated by illumination with visible light and monitored by a quartz crystal microbalance.