Synthesis of ONO-Ligated Tetrylenes Based on 2,6-bis(2-Hydroxyphenyl)pyridines: Influence of Ligand Sterics on the Structure of the Products

A series of novel tetrylenes based on three 2,6-bis(2-hydroxyphenyl)pyridines 4 a – 4 c have been obtained by the reaction of Lappert's tetrylenes E[N(SiMe₃)₂]₂ (E=Ge, Sn) with corresponding tridentate pyridine-linked phenol-based ligands. It was found that the structure of the ligand and the size of the atom of the group 14 element drastically affect the structure of the reaction product. Ligand 4 c with a bulky tert-butyl group leads to monomeric tetrylenes, while ligands with less bulky groups lead to bis-ligand derivatives of M(IV) (M=Ge, Sn) and a coordination polymer. Also, derivatives of germanium (IV) and tin (IV) were obtained by the metathesis reaction of MCl₄ (M=Ge, Sn) with lithium phenoxides. The compositions and structures of the novel compounds were established by elemental analysis and ¹H, ¹³C, ¹¹⁹Sn ( 5 – 7 ), ¹H DOSY ( 6 ) NMR spectroscopy, in the solid state by X-ray diffraction analysis (germylene 10 , stannylene 6 , Ge⁴⁺ compound 8 , Sn⁴⁺ compound 7 ) and ¹¹⁹Sn Mössbauer spectrum of tin complex 6 . All the synthesized tetrylenes are monomeric. Tetrylenes 6 and 10 were characterized by cyclic voltammetry. A study of the redox behavior of 6 , 10 by cyclic voltammetry on a glassy carbon working electrode in acetonitrile solution of 0.1 M Bu₄NPF₆ as a supporting electrolyte showed that these compounds can be both oxidized and reduced electrochemically in the accessible potential range.     

High-Porosity Metal-Organic Framework Glasses

We report a synthetic strategy to link titanium-oxo (Ti-oxo) clusters into metal-organic framework (MOF) glasses with high porosity though the carboxylate linkage. A new series of MOF glasses was synthesized by evaporation of solution containing Ti-oxo clusters Ti₁₆O₁₆(OEt)₃₂, linkers, and m-cresol. The formation of carboxylate linkages between the Ti-oxo clusters and the carboxylate linkers was confirmed by Fourier-transform infrared (FT-IR) spectroscopy. The structural integrity of the Ti-oxo clusters within the glasses was evidenced by both X-ray absorption near edge structure (XANES) and ¹⁷O magic-angle spinning (MAS) NMR. After ligand exchange and activation, the fumarate-linked MOF glass, termed Ti-Fum, showed a N₂ Brunauer–Emmett–Teller (BET) surface areas of 923 m² g⁻¹, nearly three times as high as the phenolate-linked MOF glass with the highest BET surface area prior to this report.     

Recent advances in laser self-injection locking to high-Q microresonators

The stabilization and manipulation of laser frequency by means of an external cavity are nearly ubiquitously used in fundamental research and laser applications. While most of the laser light transmits through the cavity, in the presence of some back-scattered light from the cavity to the laser, the self-injection locking effect can take place, which locks the laser emission frequency to the cavity mode of similar frequency. The self-injection locking leads to dramatic reduction of laser linewidth and noise. Using this approach, a common semiconductor laser locked to an ultrahigh-Q microresonator can obtain sub-Hertz linewidth, on par with state-of-the-art fiber lasers. Therefore it paves the way to manufacture high-performance semiconductor lasers with reduced footprint and cost. Moreover, with high laser power, the optical nonlinearity of the microresonator drastically changes the laser dynamics, offering routes for simultaneous pulse and frequency comb generation in the same microresonator. Particularly, integrated photonics technology, enabling components fabricated via semiconductor CMOS process, has brought increasing and extending interest to laser manufacturing using this method. In this article, we present a comprehensive tutorial on analytical and numerical methods of laser self-injection locking, as well a review of most recent theoretical and experimental achievements.     

Tailorable and Biocompatible Supramolecular-Based Hydrogels Featuring two Dynamic Covalent Chemistries

Dynamic covalent chemistry (DCC) has proven to be a valuable tool in creating fascinating molecules, structures, and emergent properties in fully synthetic systems. Here we report a system that uses two dynamic covalent bonds in tandem, namely disulfides and hydrazones, for the formation of hydrogels containing biologically relevant ligands. The reversibility of disulfide bonds allows fiber formation upon oxidation of dithiol-peptide building block, while the reaction between NH−NH₂ functionalized C-terminus and aldehyde cross-linkers results in a gel. The same bond-forming reaction was exploited for the “decoration” of the supramolecular assemblies by cell-adhesion-promoting sequences (RGD and LDV). Fast triggered gelation, cytocompatibility and ability to “on-demand” chemically customize fibrillar scaffold offer potential for applying these systems as a bioactive platform for cell culture and tissue engineering.