Post-synthetic modification of amine-functionalized permanently porous coordination cages.

This manuscript explores the post-synthetic modification (PSM) of amine-functionalized porous coordination cages, specifically focusing on the formation of imine bonds through reactions with aldehydes. Targeting various cage topologies, including zirconium-, magnesium-, and molybdenum-based structures, we demonstrate the tunability of cage solubility and porosity through selective functionalization where the proximity of amine groups on the parent cage impacts the extent of modification. The work highlights the reversible nature of imine formation, offering potential applications in solubility switching and mixed-metal solid synthesis.

Tunable synthesis of heteroleptic zirconium-based porous coordination cages.

Zirconium-based porous coordination cages have been widely studied and have shown to be potentially useful for many applications as a result of their tunability and stability, likely as a result of their status as a molecular equivalent to the small 8 Å tetrahedral pores of UiO-66 (Zr(μ-O)(μ-OH)(COH)). Functional groups attached to these molecular materials endow them with a range of tunable properties. While so-called multivariate MOFs containing multiple types of functional groups on different bridging ligands within a structure are common, incorporating multiple functional moieties in permanently microporous molecular materials has proved challenging.

Nickel-Catalyzed Atroposelective Cross-Electrophile Coupling of Aryl Halides: A General and Practical Route to Diverse MOP-Type Ligands.

We report a highly cross- and atroposelective coupling between -(chloro)arylphosphine oxides and -(bromo)aryl ethers. This previously unknown asymmetric nickel-catalyzed reaction offers a direct route to highly enantioenriched axially chiral biaryl monophosphine oxides that are difficult to access by other means. These products can be readily reduced to generate chiral MOP-type ligands bearing complex skeletal backbones.

Helical twists and β-turns in structures at serine-proline sequences: Stabilization of cis-proline and type VI β-turns via C-H/O interactions.

Structures at serine-proline sites in proteins were analyzed using a combination of peptide synthesis with structural methods and bioinformatics analysis of the PDB. Dipeptides were synthesized with the proline derivative (2S,4S)-(4-iodophenyl)hydroxyproline [hyp(4-I-Ph)]. The crystal structure of Boc-Ser-hyp(4-I-Ph)-OMe had two molecules in the unit cell.

Crystal structure of ()-5-(3-acetyl-5-chloro-2-ethoxy-6-fluorophenyl)-2-oxazolidinone.

The structure of ()-5-(3-acetyl-5-chloro-2-ethoxy-6-fluorophenyl)-2-oxazolidinone, CHClFNO, at 100 K has monoclinic (2) symmetry. The compound has a polymeric structure propagated by a screw axis parallel to the axis with N-H⋯O hydrogen bonding. It is of inter-est with respect to efforts in the synthesis of a candidate anti-cancer drug, parsaclisib.

Influence of Controlled Chirality on the Crystallization of Maleimide-Functionalized 3,4-Ethylenedioxythiophene (EDOT-MA) Monomers.

Conjugated poly(alkoxythiophenes) such as poly(3,4-ethylenedioxythiophene) (PEDOT) have attracted considerable interest for use in a variety of applications such as biomedical devices, energy storage, and chemical sensing. Functionalized versions of the 3,4-ethylenedioxythiophene (EDOT) monomer make it possible to create polymers with properties tailored for specific applications. The maleimide functional group shows particular promise due to the wide variety of chemical modifications that it can undergo.

Increasing the stability of calixarene-capped porous cages through coordination sphere tuning.

Chemically and thermally stable permanently porous coordination cages are appealing candidates for separations, catalysis, and as the porous component of new porous liquids. However, many of these applications have not turned to microporous cages as a result of their poor solubility and thermal or hydrolytic stability. Here we describe the design and modular synthesis of iron and cobalt cages where the carboxylate groups of the bridging ligands of well-known calixarene capped coordination cages have been replaced with more basic triazole units.

Synthesis, Characterization, and Reactivity of Tris(imido)chromium(VI) Complexes.

Multiple tris(imido)chromium(VI) complexes, including neutral and ionic compounds, have been synthesized and characterized. (BuN)Cr(NHBu)Cl can be deprotonated by KN(SiMe), yielding K[(BuN)CrCl]. This tris(imido) anion undergoes nucleophilic substitution by PPh and BuNH to form (BuN)Cr(PPh) and (BuN)Cr(NHBu), respectively.

Diversification of the Carbodicarbene Class by Embedding an Anionic Component in its Scaffold.

Carbodicarbene (CDC) has become an emerging ligand in many fields due to its strong σ-donating ability. View Article and Find Full Text PDF

An Inherent Difference between Serine and Threonine Phosphorylation: Phosphothreonine Strongly Prefers a Highly Ordered, Compact, Cyclic Conformation.

Phosphorylation and dephosphorylation of proteins by kinases and phosphatases are central to cellular responses and function. The structural effects of serine and threonine phosphorylation were examined in peptides and in proteins, by circular dichroism, NMR spectroscopy, bioinformatics analysis of the PDB, small-molecule X-ray crystallography, and computational investigations. Phosphorylation of both serine and threonine residues induces substantial conformational restriction in their physiologically more important dianionic forms.

Binuclear Macrocyclic Silver(I) Complex of a Bis(carbone) Pincer Ligand: Synthesis and Application as a Carbone-Transfer Agent.

A facile synthesis of a binuclear Ag complex of a bis(carbone) ligand and its application as a carbone-transfer agent for the generation of other transition-metal complexes of Au (), Ni (), and Pd () is presented. Complex was synthesized through multiple synthetic routes under mild reaction conditions using the tetracationic [H][OTf·Cl] precursor salt, the dicationic [H][OTf] ylide salt, and the free ligand . The first two synthesis routes require no prior isolation of the air-, moisture-, and temperature-sensitive free ligand , thus affording complex with high yield and purity.

Molybdenum(III) Amidinate: Synthesis, Characterization, and Vapor Phase Growth of Mo-Based Materials.

The synthesis, characterization, and thermogravimetric analysis of tris(,'-di-isopropylacetamidinate)molybdenum(III), Mo(iPr-AMD), are reported. Mo(iPr-AMD) is a rare example of a homoleptic mononuclear complex of molybdenum(III) and fills a longstanding gap in the literature of transition metal(III) trisamidinate complexes. Thermogravimetric analysis (TGA) reveals excellent volatilization at elevated temperatures, pointing to potential applications as a vapor phase precursor for higher temperature atomic layer deposition (ALD), or chemical vapor deposition (CVD) growth of Mo-based materials.

Rapid post-synthetic modification of porous coordination cages with copper-catalyzed click chemistry.

Novel cobalt calixarene-capped and zirconium-based porous coordination cages were prepared with alkyne and azide functionality to leverage post-synthetic modification by click chemistry. While the calixarene-capped cages showed impressive stability when exposed to the most straightforward copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC) reaction conditions with copper(II) sulfate and sodium ascorbate as the reducing agent, milder reaction conditions were necessary to perform analogous CuAAC reactions on zirconium-based cages. Reaction kinetics were monitored by IR spectroscopy, confirming rapid reaction times (<3 hours).

Mapping the influence of ligand electronics on the spectroscopic and O sensitization characteristics of Pd(II) biladiene complexes bearing phenyl-alkynyl groups at the 2- and 18-positions.

Photodynamic therapy (PDT) is a promising treatment for certain cancers that proceeds sensitization of ground state O to generate reactive O. Classic macrocyclic tetrapyrrole ligand scaffolds, such as porphyrins and phthalocyanines, have been studied in detail for their O photosensitization capabilities. Despite their compelling photophysics, these systems have been limited in PDT applications because of adverse biological side effects.

Multi-technique structural analysis of zinc carboxylates (soaps).

A series of medium- and long-chain zinc carboxylates (zinc octanoate, zinc nonanoate, zinc decanoate, zinc undecanoate, zinc dodecanoate, zinc pivalate, zinc stearate, zinc palmitate, zinc oleate, and zinc azelate) was analyzed by ultra-high-field Zn NMR spectroscopy up to 35.2 T, as well as C NMR and FTIR spectroscopy. We also report the single-crystal X-ray diffraction structures of zinc nonanoate, zinc decanoate, and zinc oleate-the first long-chain carboxylate single-crystals to be reported for zinc.

Porous Salts as Platforms for Heterogeneous Catalysis.

The preparation of a new class of reactive porous solids, prepared via straightforward salt metathesis reactions, is described here. Reaction of the dimethylammonium salt of a magnesium-based porous coordination cage with the chloride salt of [Cr Cl(Me cyclam)] affords a porous solid with concomitant removal of dimethylammonium chloride. The salt consists of the ions combined in the expected ratio based on their charge as confirmed by UV-vis and X-ray photoelectron spectroscopies, ion chromatography (IC), and inductively coupled plasma mass spectrometry (ICP-MS).

Photoredox-Nickel Dual-Catalyzed -Alkylation of Secondary Nitroalkanes: Access to Sterically Hindered α-Tertiary Amines.

The preparation of tertiary nitroalkanes via the nickel-catalyzed alkylation of secondary nitroalkanes using aliphatic iodides is reported. Previously, catalytic access to this important class of nitroalkanes via alkylation has not been possible due to the inability of catalysts to overcome the steric demands of the products. However, we have now found that the use of a nickel catalyst in combination with a photoredox catalyst and light leads to much more active alkylation catalysts.

Anion Binding as a Strategy for the Synthesis of Porous Salts.

Porous salts have recently emerged as a promising new class of ultratunable permanently microporous solids. These adsorbents, which were first reported as ionic solids based on porous cations and anions, can be isolated from a wide variety of charged, permanently porous coordination cages. A challenge in realizing the full tunability of such systems, however, lies in the fact that the majority of coordination cages for which surface areas have been reported are comprised of charge-balanced inorganic and organic building blocks that result in neutral cages.

Isocorrole-Loaded Polymer Nanoparticles for Photothermal Therapy under 980 nm Light Excitation.

Photothermal therapy (PTT) is a promising treatment option for diseases, including cancer, arthritis, and periodontitis. Typical photothermal agents (PTAs) absorb light in the near-infrared (NIR)-I region of 650-900 nm with a predominant focus around 800 nm, as these wavelengths are minimally absorbed by water and blood in the tissue. Recently, interest has grown in developing nanomaterials that offer more efficient photothermal conversion and that can be excited by light close to or within the NIR-II window of 1000-1700 nm, which offers less absorption by melanin.