Fluorinated Azobenzenes Switchable with Red Light.

Molecular photoswitches triggered with red or NIR light are optimal for photomodulation of complex biological systems, including efficient penetration of the human body for therapeutic purposes ("therapeutic window"). Yet, they are rarely reported, and even more rarely functional under aqueous conditions. In this work, fluorinated azobenzenes are shown to exhibit efficient E→Z photoisomerization with red light (PSS660nm >75 % Z) upon conjugation with unsaturated substituents. Initially demonstrated for aldehyde groups, this effect was also observed in a more complex structure by incorporating the chromophore into a cyclic dipeptide with propensity for self-assembly. Under physiological conditions, the latter molecule formed a supramolecular material that reversibly changed its viscosity upon irradiation with red light. Our observation can lead to design of new photopharmacology agents or phototriggered materials for in vivo use.

Protection-Group-Free Synthesis of Sequence-Defined Macromolecules via Precision λ-Orthogonal Photochemistry.

An advanced light-induced avenue to monodisperse sequence-defined linear macromolecules via a unique photochemical protocol is presented that does not require any protection-group chemistry. Starting from a symmetrical core unit, precision macromolecules with molecular weights up to 6257.10 g mol-1 are obtained via a two-monomer system: a monomer unit carrying a pyrene functionalized visible light responsive tetrazole and a photo-caged UV responsive diene, enabling an iterative approach for chain growth; and a monomer unit equipped with a carboxylic acid and a fumarate. Both light-induced chain growth reactions are carried out in a λ-orthogonal fashion, exciting the respective photosensitive group selectively and thus avoiding protecting chemistry. Characterization of each sequence-defined chain (size-exclusion chromatography (SEC), high-resolution electrospray ionization mass spectrometry (ESI-MS), and NMR spectroscopy), confirms the precision nature of the macromolecules.

In Situ RheoNMR Correlation of Polymer Segmental Mobility with Mechanical Properties during Hydrogel Synthesis.

Understanding polymer gelation over multiple length-scales is crucial to develop advanced materials. An experimental setup is developed that combines rheological measurements with simultaneous time-domain 1 H NMR relaxometry (TD-NMR) techniques, which are used to study molecular motion (<10 nm) in soft matter. This so-called low-field RheoNMR setup is used to study the impact of varying degrees of crosslinking (DC) on the gelation kinetics of acrylic acid (AAc) and N,N'-methylene bisacrylamide (MBA) free radical crosslinking copolymerization. A stretched exponential function describes the T2 relaxation curves throughout the gelation process. The stretching exponent ß decreases from 0.90 to 0.67 as a function of increasing DC, suggesting an increase in network heterogeneity with a broad T2 distribution at higher DC. The inverse correlation of the elastic modulus G' with T2 relaxation times reveals a pronounced molecular rigidity for higher DC at early gelation times, indicating the formation of inelastic, rigid domains such as crosslinking clusters. The authors further correlate G' with the polymer concentration during gelation using a T1 filter for solvent suppression. A characteristic scaling exponent of 2.3 is found, which is in agreement with theoretical predictions of G' based on the confining tube model in semi-dilute entangled polymer solutions.

Reversible photodissipation of composite photochromic azobenzene-alginate supramolecular hydrogels.

Supramolecular smart materials can quickly elicit macroscopic changes upon external stimulation. Here we report that an azobenzene-containing cyclic dipeptide can form composite supramolecular hydrogels with alginate based on the charge complementarity, at lower loading than the critical gelation concentrations of either component. The gels can reversibly dissipate to fluids with UV light. They can also encapsulate and photorelease fluorescent cargo. Upon treatment of the gels with aqueous calcium salts, the alginate component is permanently cross-linked and the photochromic component is solubilized.

Reversible and Stable Hemiaminal Hydrogels from Polyvinylamine and Highly Reactive and Selective Bis(N-acylpiperidone)s.

Water-soluble bis(N-acylpiperidone)s with aldehyde-like reactivity are reported to react rapidly with polyvinylamine at room temperature, providing unprecedented clean reaction products. Unlike most amine/ketone reactions that result in arbitrary mixtures of imines, aminals, hemiaminals, or hydrates, in the present study hemiaminals, aminals, or hemiaminal/aminal mixtures are exclusively found. Detailed NMR spectroscopy of solutions, gels, and solids, aided by model reactions, reveals that the hemiaminal/aminal ratio depends on pH, water content, and cross-linking density. Network formation is fully reversible upon changes in pH, with the resulting moduli from rheology spanning almost 3 orders of magnitude. The self-healing ability of the system is probed by rheology as well, demonstrating maintained material properties of fractured and healed samples. The unusually clean, fast, and reversible chemistry highlights bispiperidones as a class of efficient building blocks with unprecedented possibilities in dynamic covalent chemistry.

Phosphine-substituted 1,2,3-triazoles as P,C- and P,N-ligands for photoluminescent coinage metal complexes.

A series of homo- and hetero-polynuclear coinage metal complexes based on a phosphine-substituted 1,2,3-triazole system is presented. Besides the P,N-ligand 1-benzyl-4-(diphenylphosphanyl)-1H-1,2,3-triazole (LPN), the P,C-donor ligand 1-benzyl-4-(diphenylphosphanyl)-3-methyl-1H-1,2,3-triazolium (LPCH+), featuring a potential mesoionic carbene moiety, was obtained by methylation of LPN. Starting from the monogold chloride complexes AuCl(LPN/LPC), the syntheses of a heterotrinuclear Au2Cu complex as well as a digold carbene complex are described. The multinuclear complexes show metallophilic interactions. Their photophysical properties were investigated by temperature-dependent photoluminescence (PL) measurements. In particular, the digold complex shows interesting PL properties including narrow exciton peaks arising in the excitation and emission spectra below 50 K. These might be related to the molecular 'chains' in the crystal structure of the digold complex, formed by phenyl ligand stacking.