Power‐to‐Syngas: An Enabling Technology for the Transition of the Energy System?

Power‐to‐X concepts promise a reduction of greenhouse gas emissions simultaneously guaranteeing a safe energy supply even at high share of renewable power generation, thus becoming a cornerstone of a sustainable energy system. Power‐to‐syngas, that is, the electrochemical conversion of steam and carbon dioxide with the use of renewably generated electricity to syngas for the production of synfuels and high‐value chemicals, offers an efficient technology to couple different energy‐intense sectors, such as “traffic and transportation” and “chemical industry”. Syngas produced by co‐electrolysis can thus be regarded as a key‐enabling step for a transition of the energy system, which offers additionally features of CO₂‐valorization and closed carbon cycles. Here, we discuss advantages and current limitations of low‐ and high‐temperature co‐electrolysis. Advances in both fundamental understanding of the basic reaction schemes and stable high‐performance materials are essential to further promote co‐electrolysis.     

Hexaazatriphenylene (HAT) versus tri‐HAT: The Bigger the Better?

A new hexaazatriphenylene (HAT) derivative formed by the fusion of three HAT units has been prepared and its electronic and molecular structures have been fully characterized by optical and vibrational Raman spectroscopy, electrochemistry, solid-state UV and inverse photoemission spectroscopy (UPS and IPES), and by quantum-chemical calculations. A comparative HAT versus tri-HAT study was performed. The fusion of three HAT molecules causes modifications in the optical and electrochemical properties consistent with enhanced π-electron delocalization attained in a bigger planar core. Such combined experimental and theoretical studies are useful to balance chemical design with supramolecular engineering directed to find enhanced characteristics for new organic semiconductor applications.     

Oxyluciferin Photoacidity: The Missing Element for Solving the Keto–Enol Mystery?

The oxyluciferin family of fluorophores has been receiving much attention from the research community and several systematic studies have been performed in order to gain more insight regarding their photophysical properties and photoprotolytic cycles. In this minireview, we summarize the knowledge obtained so far and define several possible lines for future research. More importantly, we analyze the impact of the discoveries on the firefly bioluminescence phenomenon made so far and explain how they re‐open again the discussion regarding the identity (keto or enol species) of the bioluminophore.     

Electronic Bond‐to‐Bond Fluxes in Pericyclic Reactions: Synchronous or Asynchronous?

One at a time or all at once? Electronic fluxes during a pericyclic reaction in the electronic ground state--exemplified for the degenerate Cope rearrangement of semibullvalene--may proceed either synchronously or asynchronously. Quantum simulations show that the mechanism is determined by the preparation of the reactants, for example, synchronous at cryogenic temperatures (tunneling) but asynchronous when induced by selective laser pulses (with energy over the barrier).     

Multicenter Homogeneous Dendritic Catalysts: The Higher the Generation,the Better the Reactivity and Selectivity? – A Comparative Study of the Catalytic Efficiency of Dendrimeric [1,1′‐Binaphthalene]‐2,2′‐diol‐Derived Catalysts

The G0 and G1 generations of optically active, multicenter 1,1′‐binaphthalene‐based dendritic ligands 4 and 5 constructed on a rigid oligo(arylene) framework were prepared by divergent synthesis. Their corresponding aluminum complexes 1 and 2 , respectively, were shown to possess slightly better reactivity and enantioselectivity than those of a monomeric 1,1′‐binaphthalene catalyst 3 in the Diels–Alder reaction between cyclopentadiene and 3‐[(E)‐but‐2‐enoyl]‐oxazolidin‐2‐one.     

Does one‐photon photocyclization of trans‐diarylethylenes involve adiabatic trans‐to‐cis photoisomerization? potential energy surface calculations for 1‐styrylnaphthalene

Potential energy surface (PES) for 1‐styrylnaphthalene was calculated by PM3 method for the S₀ state and PM3‐CI(2x2) method with configuration interaction for the S₁ state. Scanning PES along both isomerization and cyclization reaction coordinates enabled to reveal the minimum energy path (MEP) with low barriers on the S₁ PES from E‐isomer to dihydrocyclophotoproduct (DHP). This is consistent with formation of the photocyclization product in one‐photon process during irradiation of E‐isomer. Additionally, the MEP was found to bypass the coordinate region of Z‐isomer, i.e. one‐photon E‐isomer‐to‐DHP photocyclization does not demand participation of the excited Z‐isomer. Therefore, adiabatic trans‐to‐cis isomerization is likely not an intermediate stage on the E‐isomer photocyclization pathway, and experimentally observed one‐photon formation of the DHP from the E‐isomer is likely not an evidence for adiabatic trans‐to‐cis photoisomerization, as it is usually assumed. According to the results obtained, two photochemical reactions of E‐isomer, photoisomerization to Z‐isomer and photocyclization to DHP, are not consecutive but parallel reactions with branching at perpendicular conformer on the S₁ PES. © 2012 Wiley Periodicals, Inc.     

One‐ or Two‐Electron Transfer? The Ambiguous Nature of the Discharge Products in Sodium–Oxygen Batteries

Rechargeable lithium–oxygen and sodium–oxygen cells have been considered as challenging concepts for next‐generation batteries, both scientifically and technologically. Whereas in the case of non‐aqueous Li/O₂ batteries, the occurring cell reaction has been unequivocally determined (Li₂O₂ formation), the situation is much less clear in the case of non‐aqueous Na/O₂ cells. Two discharge products, with almost equal free enthalpies of formation but different numbers of transferred electrons and completely different kinetics, appear to compete, namely NaO₂ and Na₂O₂. Cells forming either the superoxide or the peroxide have been reported, but it is unclear how the cell reaction can be influenced for selective one‐ or two‐electron transfer to occur. In this Minireview, we summarize available data, discuss important control parameters, and offer perspectives for further research. Water and proton sources appear to play major roles.     

A Carbon Nanohorn?Porphyrin Supramolecular Assembly for Photoinduced Electron‐Transfer Processes

A supramolecular assembly of zinc porphyrin? carbon nanohorns ( CNH s) was constructed in a polar solvent. An ammonium cation was covalently connected to the CNH through a spacer (sp) ( CNH ‐sp‐NH₃⁺) and bound to a crown ether linked to a zinc porphyrin (Crown? ZnP). Nanohybrids CNH ‐sp‐NH₃⁺;Crown? ZnP and CNH ‐sp‐NH₃⁺ were characterized by several techniques, such as high‐resolution transmission electron microscopy, thermogravimetric analysis, X‐ray photoelectron spectroscopy, and Raman spectroscopy. The photoinduced electron‐transfer processes of the nanohybrids have been confirmed by using time‐resolved absorption and fluorescence measurements by combining the steady‐state spectral data. Fluorescence quenching of the ZnP unit by CNH ‐sp‐NH₃⁺ has been observed, therefore, photoinduced charge separation through the excited singlet state of the ZnP unit is suggested for the hybrid material, CNH ‐sp‐NH₃⁺;Crown? ZnP. As transient absorption spectral experiments reveal the formation of the radical cation of the ZnP unit, electron generation is suggested as a counterpart of the charge‐separation on the CNH s; such an electron on the CNH s is further confirmed by migrating to the hexylviologen dication (HV²⁺). Accumulation of the electron captured from HV^.+ is observed as electron pooling in solution in the presence of a hole‐shifting reagent. Photovoltaic performance with moderate efficiency is confirmed for CNH‐ sp‐NH₃⁺;Crown? ZnP deposited onto nanostructured SnO₂ films.     

Ketone–Alcohol Hydrogen‐Transfer Equilibria: Is the Biooxidation of Halohydrins Blocked?

To ensure the quasi‐irreversibility of the oxidation of alcohols coupled with the reduction of ketones in a hydrogen‐transfer (HT) fashion, stoichiometric amounts of α‐halo carbonyl compounds have been employed as hydrogen acceptors. The reason that these substrates lead to quasi‐quantitative conversions has been tacitly attributed to both thermodynamic and kinetic effects. To provide a clear rationale for this behavior, we investigate herein the redox equilibrium of a selected series of ketones and 2‐propanol by undertaking a study that combines experimental and theoretical approaches. First, the activity of the (R)‐specific alcohol dehydrogenase from Lactobacillus brevis (LBADH) with these substrates was studied. The docking of acetophenone/(R)‐1‐phenyethanol and α‐chloroacetophenone/(S)‐2‐chloro‐1‐phenylethanol in the active site of the enzyme confirms that there seems to be no structural reason for the lack of reactivity of halohydrins. This assumption is confirmed by the fact that the corresponding aluminum‐catalyzed Meerwein–Ponndorf–Verley–Oppenauer (MPVO) reactions afford similar conversions to those obtained with LBADH, showing that the observed reactivity is independent of the catalyst employed. While the initial rates of the enzymatic reductions and the IR ν(C?O) values contradict the general belief that electron‐withdrawing groups increase the electrophilicity of the carbonyl group, the calculated ΔG values of the isodesmic redox transformations of these series of ketones/alcohols with 2‐propanol/acetone support the thermodynamic control of the reaction. As a result, a general method to predict the degree of conversion obtained in the HT‐reduction process of a given ketone based on the IR absorption band of the carbonyl group is proposed, and a strategy to achieve the HT oxidation of halohydrins is also shown.     

Diketopyrrolopyrrole?Thiophene‐Based Acceptor–Donor–Acceptor Conjugated Materials for High‐Performance Field‐Effect Transistors

We report the synthesis, morphology, and field‐effect‐transistor (FET) characteristics of new acceptor–donor–acceptor conjugated materials that consist of diketopyrrolopyrrole (DPP) acceptor groups and one of four different thiophene moieties, that is, dithiophene (2T), thieno[3,2‐b]‐thiophene (TT), dithieno[3,2‐b:2′,3′‐d]‐thiophene (DTT), and 5,5′′′‐di‐(2‐ethylhexyl)‐[2,3′;5′,2′′;4′′,2′′′]quaterthiophene (4T). The optical band gaps of the as‐prepared materials are smaller than 1.7 eV, which is attributed to the strong intramolecular charge transfer and the backbone coplanarity of the thiophene moieties. The order of both crystallinity and FET mobility (×10^?2–×10^?4 cm² V^?1 s^?1) is TT2DPP > 4T2DPP > 2T2DPP >DTT2DP, which differ in the structure of the π‐conjugated cores and core symmetry. Well‐ordered intermolecular chain packing was confirmed by the GIXD and AFM results. In particular, the FET hole mobility of TT2DPP was further improved to 0.1 cm² V^?1 s^?1, which was attributed to the well‐interconnected structure through solution‐shearing. These experimental results suggest the potential applications of the new DPP? thiophene? DPP conjugated materials for organic electronic devices.     

Counterion Effects on the Columnar Mesophases of Triphenylene‐Substituted [18]Crown‐6 Ethers: Is Flatter Better?

The twisted lateral tetraalkyloxy ortho‐terphenyl units in dibenzo[18]crown‐6 ethers 1 a – f were readily converted into the flat tetraalkyloxytriphenylene systems 2 a – f by oxidative cyclization with FeCl₃ in nitromethane. Reactions of the latter with potassium salts gave complexes KX ?2 , which displayed mesomorphic properties. The aromatization increased both the clearing and melting points; the mesophase stabilities, however, were mainly influenced by the respective anions upon complexation with various potassium salts. In contrast, the alkyl chain lengths played only a secondary role. Among the potassium complexes of triphenylene‐substituted crown ethers KX ?2 , only those with the soft anions I^? and SCN^? displayed mesophases with expanded phase temperature ranges of 93 °C and 132 °C (for KX ?2 e ), respectively, as compared to the corresponding o‐terphenyl‐substituted crown ether complexes KI ?1 e (ΔT=51 °C) and KSCN ?1 e (plastic crystal phase). Anions such as Br^?, Cl^?, and F^? decreased the mesophase stability, and PF₆^? led to complete loss of the mesomorphic properties of KPF₆ ?2 although not for KPF₆ ?1 . For crown ether complexes KX ?2 (X=F, Cl, Br, I, BF₄, and SCN), columnar rectangular mesophases of different symmetries (c2 mm, p2 mg, and p2 gg) were detected. In contrast to findings for the twisted o‐terphenyl crown ether complexes KX ?1 , the complexation of the flat triphenylene crown ethers 2 with KX resulted in the formation of organogels. Characterization of the organogel of KI ?2 e in CH₂Cl₂ revealed a network of fibers.     

The Barton Reaction: Can a More Tenable Pathway Be Hypothesized for the Formation of Nitrosoalkyl Derivatives?

Herein, we report that in the formation of nitrosoalkyl derivatives during the photolysis of alkyl nitrites, the formation of the intermediate alkyl alkoxy nitroxide, due to the trapping of alkyl radicals by the starting nitrite, is the key step of the entire process. In fact, these nitroxides, detectable by EPR spectroscopy, decay to the final nitroso derivatives under thermodynamic control. In light of this, the Barton reaction mechanism has been reviewed. The nitrosoalkyl derivatives, or the hydroxamic acids when steroids are involved, have now to be considered as the ending products of the entire process and not, unless a very high concentration of NO is present in the medium, the result of a direct reaction of NO with the alkyl radical, as is commonly accepted.     

Are Triphenylamine‐Functionalized or Carbazole‐Functionalized Iridium Complexes the More Effective Phosphorescent Materials? A Theoretical Perspective

The ground and excited states, charge injection/transport, and phosphorescence properties of eleven carbazole‐ and triphenylamine‐functionalized Ir^III complexes were investigated by using the DFT method. By analyzing the spin–orbit coupling (SOC) matrix elements, radiative decay rate constants k_r, and the electronic structures and energies at the ${{\rm{S}}_{\rm{0}}^{{\rm{opt}}} }$ and ${{\rm{T}}_{\rm{1}}^{{\rm{opt}}} }$ states, it was possible to rationalize the order of the experimental phosphorescence quantum yields of a series of Ir^III complexes and to predict that [Ir(Nph‐2‐Cz‐tz)₃] has a higher phosphorescence quantum yield than [Ir(TPA‐tz)₃] (TPA=triphenylamine, tz=thiazolyl, Cz=carbazole, Nph=N‐phenyl). Carbazole‐functionalized Ir^III complexes were shown to be efficient phosphorescent materials that have not only fast but also balanced electron/hole‐transport performance as well as high phosphorescence quantum yields. The phosphorescence emission spectra can be modulated by modifying or replacing a pyridyl substituent.     

The Liebeskind–Srogl C?C Cross‐Coupling Reaction

New kid on the block : The cross‐coupling of thioorganic compounds with boronic acids under neutral conditions in the presence of catalytic palladium(0) and a stoichiometric amount of a copper(I) oxygenate has emerged as a very useful method for the construction of C C bonds (see scheme). This intriguing and mechanistically unprecedented base‐free coupling has distinct advantages, in particular when traditional Pd⁰‐catalyzed cross‐coupling is not possible.

     

Is it True That the Normal Valence‐Length Correlation Is Irrelevant for Metal–Metal Bonds?

The most intriguing feature of metal–metal bonds in inorganic compounds is an apparent lack of correlation between the bond order and the bond length. In this study, we combine a variety of literature data obtained by quantum chemistry and our results based on the empirical bond valence model (BVM), to confirm for the first time the existence of a normal exponential correlation between the effective bond order (EBO) and the length of the metal–metal bonds. The difference between the EBO and the formal bond order is attributed to steric conflict between the (TM)_n cluster (TM=transition metal) and its environment. This conflict, affected mainly by structural type, should cause high lattice strains, but electron redistribution around TM atoms, evident from the BVM calculations, results in a full or partial strain relaxation.