Light- and temperature-assisted spin state annealing: accessing the hidden multistability

Among responsive multistable materials, spin crossover (SCO) systems are of particular interest for stabilizing multiple spin states with various stimulus inputs and physical outputs. Here, in a 2D Hofmann-type coordination polymer, [Fe(isoq)₂{Au(CN)₂}₂] (isoq = isoquinoline), a medium-temperature annealing process is introduced after light/temperature stimulation, which accesses the hidden multistability of the spin state. With the combined effort of magnetic, crystallographic and Mössbauer spectral investigation, these distinct spin states are identified and the light- and temperature-assisted transition pathways are clarified. Such excitation-relaxation and trapping-relaxation joint mechanisms, as ingenious interplays between the kinetic and thermodynamic effects, uncover hidden possibilities for the discovery of multistable materials and the development of multistate intelligent devices.

Two new two-stage manipulation protocols, namely light- and temperature-assisted spin state annealing (LASSA/TASSA), are applied to a spin crossover coordination polymer, [Fe(isoq)₂{Au(CN)₂}₂], revealing the hidden multistability of spin states.     

Facile and efficient synthesis of 6-(hydroxymethyl)purines

[reaction: see text] A facile and efficient methodology of the synthesis of 6-(hydroxymethyl)purine derivatives (bases and nucleosides) was developed based on Pd-catalyzed cross-coupling reactions of 6-halopurines with acyloxymethylzinc iodides followed by deprotection. Several title compounds are inhibitors of adenosine deaminase and exert cytostatic activity.     

Design, synthesis, and evaluation of a biomimetic artificial photolyase model

Two new artificial photolyase models that recognize pyrimidine dimers in protic and aprotic organic solvents as well as in water through a combination of charge and hydrogen-bonding interactions and use a mimic of the flavine to achieve repair through reductive photoinduced electron transfer are presented. Fluorescence and NMR titration studies show that it forms a 1:1 complex with pyrimidine dimers with binding constants of approximately 10(3) M(-1) in acetonitrile or methanol, while binding constants in water at pH 7.2 are slightly lower. Excitation of the complex with visible light leads to clean and rapid cycloreversion of the pyrimidine dimer through photoinduced electron transfer catalysis. The reaction in water is significantly faster than in organic solvents. The reaction slows down at higher conversions due to product inhibition.     

Synthesis of enantiomerically pure (purin-6-yl)phenylalanines and their nucleosides, a novel type of purine-amino acid conjugates

[Chemical reaction: See text] Enantiomerically or diastereomerically pure 4-(purin-6-yl)phenylalanines, a novel type of stable amino acid-purine conjugates, were synthesized by palladium-catalyzed cross-coupling reactions of protected 4-boronophenylalanines or 4-(trimethylstanyl)phenylalanines with diverse 6-halopurines (9-benzyl-6-halopurines and 9-(tetrahydropyran-2-yl)-6-halopurines as well as acyl- and silyl-protected 6-halopurine ribonucleosides and 2-deoxyribonucleosides). Free purine bases and nucleosides bearing (S)- or (R)-phenylalanine in position 6 were obtained after complete deprotection of the products of cross-coupling reactions. Reactivity trends for both of these cross-coupling and deprotection protocols have been compared in terms of practicability, efficiency, and stereoselectivity.     

Flavin–cyclodextrin conjugates: effect of the structure on the catalytic activity in enantioselective sulfoxidations

A series of flavin–cyclodextrin conjugates has been prepared and tested in the enantioselective oxidations of prochiral aromatic and aliphatic sulfides with hydrogen peroxide. The newly prepared conjugates contain isoalloxazinium or alloxazinium moieties attached to the primary rim of α- and β-cyclodextrins at the C-6 positions. In addition, flavinium units were attached to the secondary rim of the β-cyclodextrin macrocycle. The relationship between the structural features and the catalytic performance of the conjugates, including those recently reported by us, was analyzed. The rate and enantioselectivity of the sulfoxidations catalyzed by flavin–cyclodextrin conjugates are influenced mainly by the size of the cyclodextrin cavity, the type of flavin unit (alloxazine or isoalloxazine), and by the relative orientation of the flavin and cyclodextrin moieties.     

Phosphorus and Halogen Co‐Doped Graphene Materials and their Electrochemistry

Doping of graphene materials with heteroatoms is important as it can change their electronic and electrochemical properties. Here, graphene is co‐doped with n‐type dopants such as phosphorus and halogen (Cl, Br, I). Phosphorus and halogen are introduced through the treatment of graphene oxide with PX₃ gas (PCl₃, PBr₃, and PI₃). Graphene oxides are prepared through chlorate and permanganate routes. Detailed chemical and structural characterization demonstrates that the graphene sheets are covered homogeneously by phosphorus and halogen atoms. It is found that the amount of phosphorus and halogen introduced depends on the graphene oxide preparation method. The electrocatalytic effect of the resulting co‐doped materials is demonstrated for industrially relevant electrochemical reactions such as the hydrogen evolution and oxygen reduction reactions.     

Modified Guanines as Constituents of Smart Ligands for Nucleic Acid Quadruplexes

Repetitive guanine‐rich nucleic acid sequences play a crucial role in maintaining genome stability and the cell life cycle and represent potential targets for regulatory drugs. Recently, it has been demonstrated that guanine‐based ligands with a porphyrin core can be used as markers of G‐quadruplex assemblies in cell tissues. Herein, model systems of guanine‐based ligands are explored by DFT methods. The energies of formation of modified guanine tetrads and those of modified tetrads stacked on the top of natural guanine tetrads have been calculated. The interaction energy has been decomposed into contributions from hydrogen bonding, stacking, and ion coordination and a twist–rise potential energy scan has been performed to find the individual local minima. Energy decomposition analysis reveals the impact of various substituents (F, Cl, Br, I, Me, NMe₂) on individual energy terms. In addition, cooperative reinforcement in forming the modified and stacked tetrads, as well as the frontier orbitals participating in the hydrogen‐bonding framework involving the HOMO–LUMO gap between the occupied σ_HOMO on the proton‐accepting C=O and =N? groups and unoccupied σ_LUMO on the N?H groups, has been studied. The investigated systems are demonstrated to have a potential in ligand development, mainly due to stacking enhancement compared with natural guanine, which is used as a reference.     

Spatially Resolved Covalent Functionalization Patterns on Graphene

Spatially resolved functionalization of 2D materials is highly demanded but very challenging to achieve. The chemical patterning is typically tackled by preventing contact between the reagent and material, which brings various accompanying challenges. Photochemical transformation on the other hand inherently provides remote high spatiotemporal resolution using the cleanest reagent—a photon. Herein, we combine two competing reactions on a graphene substrate to create functionalization patterns on a micrometer scale via the Mitsunobu reaction. The mild reaction conditions allow introduction of covalently dynamic linkages, which can serve as reversible labels for surface‐ or graphene‐enhanced Raman spectroscopy characterization of the patterns prepared. The proposed methodology thus provides a pathway for local introduction of arbitrary functional groups on graphene.