High-fidelity Recognition of Organotrifluoroborate Anions (R−BF3−) as Designer Guest Molecules

The recognition of boron compounds is well developed as boronic acids but untapped as organotrifluoroborate anions (R−BF₃⁻). We are exploring the development of these and other designer anions as anion-recognition motifs by considering them as substituted versions of the parent inorganic ion. To this end, we demonstrate strong and reliable binding of organic trifluoroborates, R−BF₃⁻, by cyanostar macrocycles that are size-complementary to the inorganic BF₄⁻ progenitors. We find that recognition is modulated by the substituent's sterics and that the affinities are retained using the common K⁺ salts of R−BF₃⁻ anions.     

A Fujiwara-Moritani-Type Alkenylation Using a Traceless Directing Group Strategy: A Rare Example of C−C Bond Formation towards the C2-Carbon of Terminal Alkenes

Herein we report, a rhodium-catalyzed Fujiwara-Moritani-type reaction of unactivated terminal alkenes and benzoic acid derivatives bearing electron donating residues under mild conditions. The acid functionality acts as a traceless directing group delivering products alkenylated in meta-position to the electron donating substituent in contrast to the usually obtained ortho- and para-substitution in Friedel-Crafts-type reactions. Remarkably, the new C−C bond is formed to the C2 of the terminal olefin, in contrast to similar reported transformations. Initially formed mixtures of exo- and endo-double bond isomers can be efficiently isomerized to the more stable endo-products.     

Conformational Effects of Regioisomeric Substitution on the Catalytic Activity of Copper/Calix[8]arene C−S Coupling

Functionalization of the phenolic rim of p-tert-butylcalix[8]arene with phenanthroline to create a cavity leads to formation of two regioisomers. Substitution of positions 1 and 5 produces the known C_2v-symmetric regioisomer 1,5-(2,9-dimethyl-1,10-phenanthroyl)-p-tert-butylcalix[8]arene ( L^1,5 ), while substitution of positions 1 and 4 produces the C_s-symmetric regioisomer 1,4-(2,9-dimethyl-1,10-phenanthroyl)-p-tert-butylcalix[8]arene ( L^1,4 ) described herein. [ Cu(L^1,4)I ] was synthesized from L^1,4 and CuI in good yield and characterized spectroscopically. To evaluate the effect of its cavity on catalysis, Ullmann-type C−S coupling was chosen as proof-of-concept. Selected aryl halides were used, and the results compared with the previously reported Cu(I)/ L^1,5 system. Only highly activated aryl halides generate the C−S coupling product in moderate yields with the Cu(I)/ L^1,4 system. To shed light on these observations, detailed computational investigations were carried out, revealing the influence of the calix[8]arene macrocyclic morphology on the accessible conformations. The L^1,4 regioisomer undergoes a deformation that does not occur with L^1,5 , resulting in an exposed catalytic center, presumably the cause of the low activity of the former system. The 1,4-connectivity was confirmed in the solid-state structure of the byproduct [ Cu(L^1,4 − H) (CH₃CN)₂] that features Cu(I) coordinated inside a cleft defined by the macrocyclic framework.     

Directed Design of a AuI Complex with a Reduced Mesoionic Carbene Radical Ligand: Insights from 1,2,3-Triazolylidene Selenium Adducts and Extensive Electrochemical Investigations

Carbene-based radicals are important for both fundamental and applied chemical research. Herein, extensive electrochemical investigations of nine different 1,2,3-triazolylidene selenium adducts are reported. It is found that the half-wave potentials of the first reduction of the selones correlate with their calculated LUMO levels and the LUMO levels of the corresponding triazolylidene-based mesoionic carbenes (MICs). Furthermore, unexpected quasi-reversibility of the reduction of two triazoline selones, exhibiting comparable reduction potentials, was discovered. Through UV/Vis/NIR and EPR spectroelectrochemical investigations supported by DFT calculations, the radical anion was unambiguously assigned to be triazoline centered. This electrochemical behavior was transferred to a triazolylidene-type MIC-gold phenyl complex resulting in a MIC-radical coordinated Au^I species. Apart from UV-Vis-NIR and EPR spectroelectrochemical investigations of the reduction, the reduced gold-coordinated MIC radical complex was also formed in situ in the bulk through chemical reduction. This is the first report of a monodentate triazolylidene-based MIC ligand that can be reduced to its anion radical in a metal complex. The results presented here provide design principles for stabilizing radicals based on MICs.     

Structural,Magnetic and Catalytic Properties of a New Vacancy Ordered Perovskite Type Barium Cobaltate BaCoO2.67

A new vacancy ordered, anion deficient perovskite modification with composition of BaCoO_2.67 (Ba₃Co₃O₈□₁) has been prepared via a two-step heating process. Combined Rietveld analysis of neutron and X-ray powder diffraction data shows a novel ordering of oxygen vacancies not known before for barium cobaltates. A combination of neutron powder diffraction, magnetic measurements, and density functional theory (DFT) studies confirms G-type antiferromagnetic ordering. From impedance measurements, the electronic conductivity of the order of 10⁻⁴ S cm⁻¹ is determined. Remarkably, the bifunctional catalytic activity for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is found to be comparable to that of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3–y, confirming that charge-ordered anion deficient non-cubic perovskites can be highly efficient catalysts.     

Severi varieties on blow-ups of the symmetric square of an elliptic curve

We prove that certain Severi varieties of nodal curves of positive genus on general blow-ups of the twofold symmetric product of a general elliptic curve are nonempty and smooth of the expected dimension. This result, besides its intrinsic value, is an important preliminary step for the proof of nonemptiness of Severi varieties on general Enriques surfaces.     

Pyrimidoquinazolinophenanthroline Opens Next Chapter in Design of Bridging Ligands for Artificial Photosynthesis**

The synthesis and detailed characterization of a new Ru polypyridine complex containing a heteroditopic bridging ligand with previously unexplored metal-metal distances is presented. Due to the twisted geometry of the novel ligand, the resultant division of the ligand in two distinct subunits leads to steady state as well as excited state properties of the corresponding mononuclear Ru(II) polypyridine complex resembling those of prototype [Ru(bpy)₃]²⁺ (bpy=2,2'-bipyridine). The localization of the initially optically excited and the nature of the long-lived excited states on the Ru-facing ligand spheres is evaluated by resonance Raman and fs-TA spectroscopy, respectively, and supported by DFT and TDDFT calculations. Coordination of a second metal (Zn or Rh) to the available bis-pyrimidyl-like coordination sphere strongly influences the frontier orbitals, apparent by, for example, luminescence quenching. Thus, the new bridging ligand motif offers electronic properties, which can be adjusted by the nature of the second metal center. Using the heterodinuclear Ru−Rh complex, visible light-driven reduction of NAD⁺ to NADH was achieved, highlighting the potential of this system for photocatalytic applications.     

Chlorophyll‐Derived Yellow Phyllobilins of Higher Plants as Medium‐Responsive Chiral Photoswitches

The fall colors are signs of chlorophyll breakdown, the biological process in plants that generates phyllobilins. Most of the abundant natural phyllobilins are colorless, but yellow phyllobilins (phylloxanthobilins) also occur in fall leaves. As shown here, phylloxanthobilins are unique four‐stage photoswitches. Which switching mode is turned on is controlled by the molecular environment. In polar media, phylloxanthobilins are monomeric and undergo photoreversible Z/E isomerization, similar to that observed for bilirubin. Unlike bilirubin, however, the phylloxanthobilin Z isomers photodimerize in apolar solvents by regio‐ and stereospecific thermoreversible [2+2] cycloadditions from self‐assembled hydrogen‐bonded dimers. X‐ray analysis revealed the first stereostructure of a phylloxanthobilin and its hydrogen‐bonded self‐templating architecture, helping to rationalize its exceptional photoswitch features. The chemical behavior of phylloxanthobilins will play a seminal role in identifying biological roles of phyllobilins.