Redox‐Induced Spin‐State Switching and Mixed Valency in Quinonoid‐Bridged Dicobalt Complexes

The complexes [{(tmpa)Co^II}₂(μ‐L¹)^2?]²⁺ ( 1²⁺ ) and [{(tmpa)Co^II}₂(μ‐L²)^2?]²⁺ ( 2²⁺ ), with tmpa=tris(2‐pyridylmethyl)amine, H₂L¹=2,5‐di‐[2‐(methoxy)‐anilino]‐1,4‐benzoquinone, and H₂L²=2,5‐di‐[2‐(trifluoromethyl)‐anilino]‐1,4‐benzoquinone, were synthesized and characterized. Structural analysis of 2²⁺ revealed a distorted octahedral coordination around the cobalt centers, and cobalt–ligand bond lengths that match with high‐spin Co^II centers. Superconducting quantum interference device (SQUID) magnetometric studies on 1²⁺ and 2²⁺ are consistent with the presence of two weakly exchange‐coupled high‐spin cobalt(II) ions, for which the nature of the coupling appears to depend on the substituents on the bridging ligand, being antiferromagnetic for 1²⁺ and ferromagnetic for 2²⁺ . Both complexes exhibit several one‐electron redox steps, and these were investigated with cyclic voltammetry and UV/Vis/near‐IR spectroelectrochemistry. For 1²⁺ , it was possible to chemically isolate the pure forms of both the one‐electron oxidized mixed‐valent 1³⁺ and the two‐electron oxidized isovalent 1⁴⁺ forms, and characterize them structurally as well as magnetically. This series thus provided an opportunity to investigate the effect of reversible electron transfers on the total spin‐state of the molecule. In contrast to 2²⁺ , for 1⁴⁺ the metal–ligand distances and the distances within the quinonoid ligand point to the existence of two low‐spin Co^III centers, thus showing the innocence of the quintessential non‐innocent ligands L. Magnetic data corroborate these observations by showing the decrease of the magnetic moment by roughly half (neglecting spin exchange effects) on oxidizing the molecules with one electron, and the disappearance of a paramagnetic response upon two‐electron oxidation, which confirms the change in spin state associated with the electron‐transfer steps.     

Selective Uptake of Cylindrical Poly(2‐Oxazoline) Brush‐AntiDEC205 Antibody‐OVA Antigen Conjugates into DEC‐Positive Dendritic Cells and Subsequent T‐Cell Activation

To achieve specific cell targeting by various receptors for oligosaccharides or antibodies, a carrier must not be taken up by any of the very many different cells and needs functional groups prone to clean conjugation chemistry to derive well‐defined structures with a high biological specificity. A polymeric nanocarrier is presented that consists of a cylindrical brush polymer with poly‐2‐oxazoline side chains carrying an azide functional group on each of the many side chain ends. After click conjugation of dye and an anti‐DEC205 antibody to the periphery of the cylindrical brush polymer, antibody‐mediated specific binding and uptake into DEC205⁺‐positive mouse bone marrow‐derived dendritic cells (BMDC) was observed, whereas binding and uptake by DEC205^? negative BMDC and non‐DC was essentially absent. Additional conjugation of an antigen peptide yielded a multifunctional polymer structure with a much stronger antigen‐specific T‐cell stimulatory capacity of pretreated BMDC than application of antigen or polymer–antigen conjugate.     

Reactions in Nitroimidazole Triggered by Low‐Energy (0–2 eV) Electrons: Methylation at N1‐H Completely Blocks Reactivity

Low‐energy electrons (LEEs) at energies of less than 2 eV effectively decompose 4‐nitroimidazole (4NI) by dissociative electron attachment (DEA). The reactions include simple bond cleavages but also complex reactions involving multiple bond cleavages and formation of new molecules. Both simple and complex reactions are associated with pronounced sharp features in the anionic yields, which are interpreted as vibrational Feshbach resonances acting as effective doorways for DEA. The remarkably rich chemistry of 4NI is completely blocked in 1‐methyl‐4‐nitroimidazole (Me4NI), that is, upon methylation of 4NI at the N1 site. These remarkable results have also implications for the development of nitroimidazole based radiosensitizers in tumor radiation therapy.     

Electron‐Driven Self‐Assembly of Salt Nanocrystals in Liquid Helium

The self‐assembly of salt nanocrystals from chemical reactions inside liquid helium is reported for the first time. Reaction is initiated by an electron impacting a helium nanodroplet containing sodium atoms and SF₆ molecules, leading to preferential production of energetically favorable structures based on the unit cell of crystalline NaF. These favorable structures are observed as magic number ions (anomalously intense peaks) in mass spectra and are seen in both cationic and anionic channels in mass spectra, for example, (NaF)_nNa⁺ and (NaF)_nF^?. In the case of anions the self‐assembly is not directly initiated by electrons: the dominant process involves resonant electron‐induced production of metastable electronically excited He^? anions, which then initiate anionic chemistry by electron transfer.     

Ligand Effects on the Electronic Structure of Heteroleptic Antimony-Centered Radicals

We report on the structures of three unprecedented heteroleptic Sb-centered radicals [L(Cl)Ga](R)Sb^. ( 2-R , R=B[N(Dip)CH]₂ 2-B , 2,6-Mes₂C₆H₃ 2-C , N(SiMe₃)Dip 2-N ) stabilized by one electropositive metal fragment [L(Cl)Ga] (L=HC[C(Me)N(Dip)]₂, Dip=2,6-i-Pr₂C₆H₃) and one bulky B- ( 2-B ), C- ( 2-C ), or N-based ( 2-N ) substituent. Compounds 2-R are predominantly metal-centered radicals. Their electronic properties are largely influenced by the electronic nature of the ligands R, and significant delocalization of unpaired-spin density onto the ligands was observed in 2-B and 2-N . Cyclic voltammetry (CV) studies showed that 2-B undergoes a quasi-reversible one-electron reduction, which was confirmed by the synthesis of [K([2.2.2]crypt)][L(Cl)GaSbB[N(Dip)CH]₂] ([K([2.2.2]crypt)][ 2-B ]) containing the stibanyl anion [ 2-B ]⁻, which was shown to possess significant Sb−B multiple-bonding character.     

A General Pathway to Heterobimetallic Triple-Decker Complexes

A systematic study on the reactivity of the triple-decker complex [(Cp’’’Co)₂(μ,η⁴:η⁴-C₇H₈)] ( A ) (Cp’’’=1,2,4-tritertbutyl-cyclopentadienyl) towards sandwich complexes containing cyclo-P₃, cyclo-P₄, and cyclo-P₅ ligands under mild conditions is presented. The heterobimetallic triple-decker sandwich complexes [(Cp*Fe)(Cp’’’Co)(μ,η⁵:η⁴-P₅)] ( 1 ) and [(Cp’’’Co)(Cp’’’Ni)(μ,η³:η³-P₃)] ( 3 ) (Cp*=1,2,3,4,5-pentamethylcyclopentadienyl) were synthesized and fully characterized. In solution, these complexes exhibit a unique fluxional behavior, which was investigated by variable temperature NMR spectroscopy. The dynamic processes can be blocked by coordination to {W(CO)₅} fragments, leading to the complexes [(Cp*Fe)(Cp’’’Co)(μ₃,η⁵:η⁴:η¹-P₅){W(CO)₅}] ( 2 a ), [(Cp*Fe)(Cp’’’Co)(μ₄,η⁵:η⁴:η¹:η¹-P₅){(W(CO)₅)₂}] ( 2 b ), and [(Cp’’’Co)(Cp’’’Ni)(μ₃,η³:η²:η¹-P₃){W(CO)₅}] ( 4 ), respectively. The thermolysis of 3 leads to the tetrahedrane complex [(Cp’’’Ni)₂(μ,η²:η²-P₂)] ( 5 ). All compounds were fully characterized using single-crystal X-ray structure analysis, NMR spectroscopy, mass spectrometry, and elemental analysis.     

Tuning PtII-Based Donor–Acceptor Systems through Ligand Design: Effects on Frontier Orbitals,Redox Potentials,UV/Vis/NIR Absorptions,Electrochromism, and Photocatalysis

Asymmetric platinum donor–acceptor complexes [(pimp)Pt(Q²⁻)] are presented in this work, in which pimp=[(2,4,6-trimethylphenylimino)methyl]pyridine and Q²⁻=catecholate-type donor ligands. The properties of the complexes are evaluated as a function of the donor ligands, and correlations are drawn among electrochemical, optical, and theoretical data. Special focus has been put on the spectroelectrochemical investigation of the complexes featuring sulfonyl-substituted phenylendiamide ligands, which show redox-induced linkage isomerism upon oxidation. Time-dependent density functional theory (TD-DFT) as well as electron flux density analysis have been employed to rationalize the optical spectra of the complexes and their reactivity. Compound 1 ([(pimp)Pt(Q²⁻)] with Q²⁻=3,5-di-tert-butylcatecholate) was shown to be an efficient photosensitizer for molecular oxygen and was subsequently employed in photochemical cross-dehydrogenative coupling (CDC) reactions. The results thus display new avenues for donor–acceptor systems, including their role as photocatalysts for organic transformations, and the possibility to introduce redox-induced linkage isomerism in these compounds through the use of sulfonamide substituents on the donor ligands.     

Light-Activated Carbon Monoxide Prodrugs Based on Bipyridyl Dicarbonyl Ruthenium(II) Complexes

Two photoactivatable dicarbonyl ruthenium(II) complexes based on an amide-functionalised bipyridine scaffold (4-position) equipped with an alkyne functionality or a green-fluorescent BODIPY (boron-dipyrromethene) dye have been prepared and used to investigate their light-induced decarbonylation. UV/Vis, FTIR and ¹³C NMR spectroscopies as well as gas chromatography and multivariate curve resolution alternating least-squares analysis (MCR-ALS) were used to elucidate the mechanism of the decarbonylation process. Release of the first CO molecule occurs very quickly, while release of the second CO molecule proceeds more slowly. In vitro studies using two cell lines A431 (human squamous carcinoma) and HEK293 (human embryonic kidney cells) have been carried out in order to characterise the anti-proliferative and anti-apoptotic activities. The BODIPY-labelled compound allows for monitoring the cellular uptake, showing fast internalisation kinetics and accumulation at the endoplasmic reticulum and mitochondria.     

Metal/Metal Redox Isomerism Governed by Configuration

A pair of diastereomeric dinuclear complexes, [Tp′(CO)BrW{μ-η²-C,C′-κ²-S,P-C₂(PPh₂)S}Ru(η⁵-C₅H₅)(PPh₃)], in which W and Ru are bridged by a phosphinyl(thiolato)alkyne in a side-on carbon P,S-chelate coordination mode, were synthesized, separated and fully characterized. Even though the isomers are similar in their spectroscopic properties and redox potentials, the like-isomer is oxidized at W while the unlike-isomer is oxidized at Ru, which is proven by IR, NIR and EPR-spectroscopy supported by spectro-electrochemistry and computational methods. The second oxidation of the complexes was shown to take place at the metal left unaffected in the first redox step. Finally, the tipping point could be realized in the unlike isomer of the electronically tuned thiophenolate congener [Tp′(CO)(PhS)W{μ-η²-C,C′-κ²-S,P-C₂(PPh₂)S}Ru(η⁵-C₅H₅)-(PPh₃)], in which valence trapped W^III/Ru^II and W^II/Ru^III cationic species are at equilibrium.     

Ruthenium-Catalyzed Hydrogenative Degradation of End-of-Life Poly(lactide) to Produce 1,2-Propanediol as Platform Chemical

The chemical recycling of end-of-life polymers can add some value to a future circular economy. In this regard, the hydrogenative degradation of end-of-life PLA was investigated to produce 1,2-propanediol as product, which is a useful building block in polymer chemistry. In more detail, the commercially available Ru-MACHO-BH complex was applied as catalyst to degrade end-of-life PLA efficiently to 1,2-propanediol under mild conditions. After investigations of the reaction conditions a set of end-of-life PLA goods were subjected to degradation.