Fundamental Characterization,Photophysics and Photocatalysis of a Base Metal Iron(II)-Cobalt(III) Dyad

A new base metal iron-cobalt dyad has been obtained by connection between a heteroleptic tetra-NHC iron(II) photosensitizer combining a 2,6-bis[3-(2,6-diisopropylphenyl)imidazol-2-ylidene]pyridine with 2,6-bis(3-methyl-imidazol-2-ylidene)-4,4′-bipyridine ligand, and a cobaloxime catalyst. This novel iron(II)-cobalt(III) assembly has been extensively characterized by ground- and excited-state methods like X-ray crystallography, X-ray absorption spectroscopy, (spectro-)electrochemistry, and steady-state and time-resolved optical absorption spectroscopy, with a particular focus on the stability of the molecular assembly in solution and determination of the excited-state landscape. NMR and UV/Vis spectroscopy reveal dissociation of the dyad in acetonitrile at concentrations below 1 mM and high photostability. Transient absorption spectroscopy after excitation into the metal-to-ligand charge transfer absorption band suggests a relaxation cascade originating from hot singlet and triplet MLCT states, leading to the population of the ³MLCT state that exhibits the longest lifetime. Finally, decay into the ground state involves a ³MC state. Attachment of cobaloxime to the iron photosensitizer increases the ³MLCT lifetime at the iron centre. Together with the directing effect of the linker, this potentially makes the dyad more active in photocatalytic proton reduction experiments than the analogous two-component system, consisting of the iron photosensitizer and Co(dmgH)₂(py)Cl. This work thus sheds new light on the functionality of base metal dyads, which are important for more efficient and sustainable future proton reduction systems.     

Selective Detection of Carbohydrates and Their Peptide Conjugates by ESI-MS Using Synthetic Quaternary Ammonium Salt Derivatives of Phenylboronic Acids

We present new tags based on the derivatives of phenylboronic acid and apply them for the selective detection of sugars and peptide-sugar conjugates in mass spectrometry. We investigated the binding of phenylboronic acid and its quaternary ammonium salt (QAS) derivatives to carbohydrates and peptide-derived Amadori products by HR-MS and MS/MS experiments. The formation of complexes between sugar or sugar-peptide conjugates and synthetic tags was confirmed on the basis of the unique isotopic distribution resulting from the presence of boron atom. Moreover, incorporation of a quaternary ammonium salt dramatically improved the efficiency of ionization in mass spectrometry. It was found that the formation of a complex with phenylboronic acid stabilizes the sugar moiety in glycated peptides, resulting in simplification of the fragmentation pattern of peptide-derived Amadori products. The obtained results suggest that derivatization of phenylboronic acid as QAS is a promising method for sensitive ESI-MS detection of carbohydrates and their conjugates formed by non-enzymatic glycation or glycosylation.

Anion–π and Cation–π Interactions on the Same Surface

Herein, we address the question whether anion–π and cation–π interactions can take place simultaneously on the same aromatic surface. Covalently positioned carboxylate–guanidinium pairs on the surface of 4‐amino‐1,8‐naphthalimides are used as an example to explore push–pull chromophores as privileged platforms for such “ion pair–π” interactions. In antiparallel orientation with respect to the push–pull dipole, a bathochromic effect is observed. A red shift of 41 nm found in the least polar solvent is in good agreement with the 70 nm expected from theoretical calculations of ground and excited states. Decreasing shifts with solvent polarity, protonation, aggregation, and parallel carboxylate–guanidinium pairs imply that the intramolecular Stark effect from antiparallel ion pair–π interactions exceeds solvatochromic effects by far. Theoretical studies indicate that carboxylate–guanidinium pairs can also interact with the surfaces of π‐acidic naphthalenediimides and π‐basic pyrenes.     

Stereospecific 1,2-Migrations of Boronate Complexes Induced by Electrophiles

The stereospecific 1,2-migration of boronate complexes is one of the most representative reactions in boron chemistry. This process has been used extensively to develop powerful methods for asymmetric synthesis, with applications spanning from pharmaceuticals to natural products. Typically, 1,2-migration of boronate complexes is driven by displacement of an α-leaving group, oxidation of an α-boryl radical, or electrophilic activation of an alkenyl boronate complex. The aim of this article is to summarize the recent advances in the rapidly expanding field of electrophile-induced stereospecific 1,2-migration of groups from boron to sp² and sp³ carbon centers. It will be shown that three different conceptual approaches can be utilized to enable the 1,2-migration of boronate complexes: stereospecific Zweifel-type reactions, catalytic conjunctive coupling reactions, and transition metal-free sp²–sp³ couplings. A discussion of the reaction scope, mechanistic insights, and synthetic applications of the work described is also presented.     

SIMS accurate determination of matrix composition of topological crystalline insulator material Pb1 − xSnxSe

Substitutional alloy Pb_1 − xSn_xSe is a new class of electronic materials called topological crystalline insulators, which at the temperature range from 0 K to 300 K exhibit topological state at compositions in the range 0.18 < x < 0.40 (in the rock-salt structure). In this report, we present a secondary ion mass spectrometry (SIMS) analysis technique to provide accurate Pb and Sn composition based on the measurement of PbCs⁺ and SnCs⁺ cluster ions intensities. Studies of Pb_1 − xSn_xSe bulk samples with various values of x show that x/(1 − x) is linear in relation to the intensity ratio of PbCs⁺/SnCs⁺ over the range from x = 0.15 to x = 0.41. This technique allows us to obtain an accurate Sn content for multilayered heterostructures, quantum wells containing Pb_1 − xSn_xSe with different x values for each layer.     

Photoswitchable Sol–Gel Transitions and Catalysis Mediated by Polymer Networks with Coumarin-Decorated Cu24L24 Metal–Organic Cages as Junctions

Photoresponsive materials that change in response to light have been studied for a range of applications. These materials are often metastable during irradiation, returning to their pre-irradiated state after removal of the light source. Herein, we report a polymer gel comprising poly(ethylene glycol) star polymers linked by Cu₂₄L₂₄ metal–organic cages/polyhedra (MOCs) with coumarin ligands. In the presence of UV light, a photosensitizer, and a hydrogen donor, this “polyMOC” material can be reversibly switched between Cu^II, Cu^I, and Cu⁰. The instability of the MOC junctions in the Cu^I and Cu⁰ states leads to network disassembly, forming Cu^I/Cu⁰ solutions, respectively, that are stable until re-oxidation to Cu^II and supramolecular gelation. This reversible disassembly of the polyMOC network can occur in the presence of a fixed covalent second network generated in situ by copper-catalyzed azide-alkyne cycloaddition (CuAAC), providing interpenetrating supramolecular and covalent networks.     

Stapled Peptides as HIF-1α/p300 Inhibitors: Helicity Enhancement in the Bound State Increases Inhibitory Potency

Protein–protein interactions (PPIs) control virtually all cellular processes and have thus emerged as potential targets for development of molecular therapeutics. Peptide-based inhibitors of PPIs are attractive given that they offer recognition potency and selectivity features that are ideal for function, yet, they do not predominantly populate the bioactive conformation, frequently suffer from poor cellular uptake and are easily degraded, for example, by proteases. The constraint of peptides in a bioactive conformation has emerged as a promising strategy to mitigate against these liabilities. In this work, using peptides derived from hypoxia-inducible factor 1 (HIF-1α) together with dibromomaleimide stapling, we identify constrained peptide inhibitors of the HIF-1α/p300 interaction that are more potent than their unconstrained sequences. Contrary to expectation, the increased potency does not correlate with an increased population of an α-helical conformation in the unbound state as demonstrated by experimental circular dichroism analysis. Rather, the ability of the peptide to adopt a bioactive α-helical conformation in the p300 bound state is better supported in the constrained variant as demonstrated by molecular dynamics simulations and circular dichroism difference spectra.     

A Molecular Strategy to Lock‐in the Conformation of a Perylene Bisimide‐Derived Supramolecular Polymer

Locking‐in the conformation of supramolecular assemblies provides a new avenue to regulate the (opto)electronic properties of robust nanoscale objects. In the present contribution, we show that the covalent tethering of a perylene bisimide (PBI)‐derived supramolecular polymer with a molecular locker enables the formation of a locked superstructure equipped with emergent structure–function relationships. Experiments that exploit variable‐temperature ground‐state electronic absorption spectroscopy unambiguously demonstrate that the excitonic coupling between nearest neighboring units in the tethered superstructure is preserved at a temperature (371 K) where the pristine, non‐covalent assembly exists exclusively in a molecularly dissolved state. A close examination of the solid‐state morphologies reveals that the locked superstructure engenders the formation of hierarchical 1D materials which are not achievable by unlocked assemblies. To complement these structural attributes, we further demonstrate that covalently tethering a supramolecular polymer built from PBI subunits enables the emergence of electronic properties not evidenced in non‐covalent assemblies. Using cyclic voltammetry experiments, the elucidation of the potentiometric properties of the locked superstructure reveals a 100‐mV stabilization of the conduction band energy when compared to that recorded for the non‐covalent assembly.