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The bridging MeCN ligand in the dicopper(I) complexes [(DPFN)Cu 2 (μ,η 1  : η 1 -MeCN)][X] 2 (X=weakly coordinating anion, NTf 2 (1 a), FAl[OC 6 F 10 (C 6 F 5 )] 3 (1 b), Al[OC(CF 3 ) 3 ] 4 (1 c)) was replaced by white phosphorus (P 4 ) or yellow arsenic (As 4 ) to yield [(DPFN)Cu 2 (μ,η 2  : η 2 -E 4 )][X] 2 (E=P (2 a-c), As (3 a-c)). The molecular structures in the solid state reveal novel coordination modes for E 4 tetrahedra bonded to coinage metal ions. Experimental data and quantum chemical computations provide information concerning perturbations to the bonding in coordinated E 4 tetrahedra. Reactions with N-heterocyclic carbenes (NHCs) led to replacement of the E 4 tetrahedra with release of P 4 or As 4 and formation of [(DPFN)Cu 2 (μ,η 1  : η 1 - Me NHC)][X] 2 (4 a,b) or to an opening of one E-E bond leading to an unusual E 4 butterfly structural motif in [(DPFN)Cu 2 (μ,η 1  : η 1 -E 4 Dipp NHC)][X] 2 (E=P (5 a,b), E=As (6)). With a cyclic alkyl amino carbene ( Et CAAC), cleavage of two As-As bonds was observed to give two isomers of [(DPFN)Cu 2 (μ,η 2  : η 2 -As 4 Et CAAC)][X] 2 (7 a,b) with an unusual As 4 -triangle+1 unit., (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Populations experiencing negligible predation pressure are expected to evolve higher behavioral activity. However, when sexes have different expected benefits from high activity, the adaptive shift is expected to be sex-specific. Here, we compared movement activity of one cave (lack of predation) and three adjacent surface (high and diverse predation) populations of Asellus aquaticus , a freshwater isopod known for its independent colonization of several caves across Europe. We predicted 1) higher activity in cave than in surface populations, with 2) the difference being more pronounced in males as they are known for active mate searching behavior, while females are not. Activity was assessed both in the presence and absence of light. Our results supported both predictions: movement activity was higher in the cave than in the surface populations, particularly in males. Relaxed predation pressure in the cave-adapted population is most likely the main selective factor behind increased behavioral activity, but we also showed that the extent of increase is sex-specific., (© The Author(s) 2022. Published by Oxford University Press on behalf of Editorial Office, Current Zoology.)

The oxidation of [(Cp'''Co) 2 (μ,η 2  : η 2 -E 2 ) 2 ] (E=As (1), P (2); Cp'''=1,2,4-tri(tert-butyl)cyclopentadienyl) with halogens or halogen sources (I 2 , PBr 5 , PCl 5 ) was investigated. For the arsenic derivative, the ionic compounds [(Cp'''Co) 2 (μ,η 4  : η 4 -As 4 X)][Y] (X=I, Y=[As 6 I 8 ] 0.5 (3 a), Y=[Co 2 Cl 6-n I n ] 0.5 (n=0, 2, 4; 3 b); X=Br, Y=[Co 2 Br 6 ] 0.5 (4); X=Cl, Y=[Co 2 Cl 6 ] 0.5 (5)) were isolated. The oxidation of the phosphorus analogue 2 with bromine and chlorine sources yielded the ionic complexes [(Cp'''Co) 2 (μ-PBr 2 ) 2 (μ-Br)][Co 2 Br 6 ] 0.5 (6 a), [(Cp'''Co) 2 (μ-PCl 2 ) 2 (μ-Cl)][Co 2 Cl 6 ] 0.5 (6 b) and the neutral species [(Cp'''Co) 2 (μ-PCl 2 )(μ-PCl)(μ,η 1  : η 1 -P 2 Cl 3 ] (7), respectively. As an alternative approach, quenching of the dications [(Cp'''Co) 2 (μ,η 4  : η 4 -E 4 )][TEF] 2 (TEF=[Al{OC(CF 3 ) 3 } 4 ] - , E=As (8), P (9)) with KI yielded [(Cp'''Co) 2 (μ,η 4  : η 4 -As 4 I)][I] (10), representing the homologue of 3, and the neutral complex [(Cp'''Co)(Cp'''CoI 2 )(μ,η 4  : η 1 -P 4 )] (11), respectively. The use of [(CH 3 ) 4 N]F instead of KI leads to the formation of [(Cp'''Co) 2 (μ-PF 2 )(μ,η 2  : η 1  : η 1 -P 3 F 2 )] (12) and 2, thereby revealing synthetic access to polyphosphorus compounds bearing P-F groups and avoiding the use of very strong fluorinating reagents, such as XeF 2 , that are difficult to control., (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The oxidation of [(Cp*Mo) 2 (μ,η 6 :η 6 -P 6 )] (1) with halogens or halogen sources was investigated. The iodination afforded the ionic complexes [(Cp*Mo) 2 (μ,η 3 :η 3 -P 3 )(μ,η 1 :η 1 :η 1 :η 1 -P 3 I 3 )][X] (X=I 3 - , I - ) (2) and [(Cp*Mo) 2 (μ,η 4 :η 4 -P 4 )(μ-PI 2 )][I 3 ] (3), while the reaction with PBr 5 led to the complexes [(Cp*Mo) 2 (μ,η 3 :η 3 -P 3 )(μ-Br) 2 ][Cp*MoBr 4 ] (4) [(Cp*MoBr) 2 (μ,η 3 :η 3 -P 3 )(μ,η 1 -P 2 Br 3 )] (5) and [(Cp*Mo) 2 (μ-PBr 2 )(μ-PHBr)(μ-Br) 2 ] (6). The reaction of 1 with the far stronger oxidizing agent PCl 5 was followed via time- and temperature-dependent 31 P{ 1 H} NMR spectroscopy. One of the first intermediates detected at 193 K was [(Cp*Mo) 2 (μ,η 3 :η 3 -P 3 )(μ-PCl 2 ) 2 ][PCl 6 ] (8) which rearranges upon warming to [(Cp*Mo) 2 (μ-PCl 2 ) 2 (μ-Cl) 2 ] (9), [(Cp*MoCl) 2 (μ,η 3 :η 3 -P 3 )(μ-PCl 2 )] (10) and [(Cp*Mo) 2 (μ,η 4 :η 4 -P 4 )(μ-PCl 2 )][Cp*MoCl 4 ] (11), which could be isolated at room temperature. All complexes were characterized by single-crystal X-ray diffraction, NMR spectroscopy and their electronic structures were elucidated by DFT calculations., (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The importance of datasharing is of increasing concern to funding bodies and institutions. With some prescience, the radiobiology community has established datasharing infrastructures over the last two decades, including STORE; however, the utilization of these databases is disappointing. The aim of the present study was to identify the current state of datasharing amongst researchers in radiation protection, and to identify barriers to effective sharing. An electronic survey was prepared, including questions on post-publication data provision, institutional, funding agency, and journal policies, awareness of datasharing infrastructures, attitudinal barriers and technical support. The survey was sent to the members of a mailing list maintained by the EC funded CONCERT project. Responses identified that the radiation protection community shared similar concerns to other groups canvassed in earlier studies; the perceived negative impact of datasharing on competitiveness, career development and reputation, along with concern about the costs of data management. More surprising was the lack of awareness of existing datasharing platforms. We find that there is a clear need for education and training in data management and for a significant programme of improving awareness of Open Data issues. [ABSTRACT FROM AUTHOR]

Low dose hyper-radiosensitivity (HRS) and induced radioresistance (IRR) can be observed in the dose dependence of survival of many different cell lines. While surviving fraction decreases exponentially in a large-scale view, a local minimum can be found at around 0.5 Gy. Although, there is evidence that the regulation of apoptosis and DNA repair are involved in HRS and IRR, the fundamental causes of the phenomena remain unclear. The objective of the present study is to test whether the principle of minimum mutation load can provide an explanation for both low dose HRS and IRR. For this purpose, a mathematical model was elaborated considering radiation induced mutagenic DNA lesions as well as cell divisions as sources of mutations. It was presumed that cell number is in dynamic equilibrium in the tissue, the number of mutations follows Poisson distribution, and its average is proportional to absorbed dose. For each value of absorbed dose, the minimum number of mutations were computed for different surviving fractions. Then that surviving fraction was plotted that results in the lowest number of mutations. One minimum or multiple minima can be seen in the dose dependence of surviving fractions with reasonable values for the model parameters: spontaneous and radiation induced mutation rate. Although the mechanisms remain unclear, the principle of minimum mutation load provides a potential explanation for low dose HRS and IRR and for the fact that they are mostly observed in cell lines with defected DNA repair. [ABSTRACT FROM AUTHOR]

A novel reactivity of [{Cp*Cr(CO)3}2(μ,η1:1−P4)] (Cp*=C5Me5; 1) is reported, which utilizes the selective cleavage of the two P−Cr bonds and subsequently initiates a substituent exchange yielding P4 butterfly compounds. By means of NMR and IR spectroscopy studies, the successful implementation of 1 to obtain [{Cp′′′Fe(CO)2}2(μ,η1:1−P4)] (Cp′′′=C5H2tBu3; 2) and Cp′′′2P4 (3) could be confirmed, by reacting 1 with 2.0 eq. of K[Cp′′′Fe(CO)2] or NaCp′′′, respectively. Hereby, a quantitative conversion could be detected alongside the formation of 2.0 eq. of the [Cp*Cr(CO)3]− anion. Moreover, various syntheses of novel organometallic and organo‐P4 butterfly compounds were examined and first results show that the generation of different compounds should be possible. However, the isolation and stabilization of these sensitive molecules proves to be a major challenge. [ABSTRACT FROM AUTHOR]

Heterogenization of molecular catalysts via their immobilization within extended structures often results in a lowering of their catalytic properties due to a change in their coordination sphere. Metal-organic polyhedra (MOP) are an emerging class of well-defined hybrid compounds with a high number of accessible metal sites organized around an inner cavity, making them appealing candidates for catalytic applications. Here, we demonstrate a design strategy that enhances the catalytic properties of dirhodium paddlewheels heterogenized within MOP (Rh-MOP) and their three-dimensional assembled supramolecular structures, which proved to be very efficient catalysts for the selective photochemical reduction of carbon dioxide to formic acid. Surprisingly, the catalytic activity per Rh atom is higher in the supramolecular structures than in its molecular sub-unit Rh-MOP or in the Rh-metal-organic framework (Rh-MOF) and yields turnover frequencies of up to 60 h -1 and production rates of approx. 76 mmole formic acid per gram of the catalyst per hour, unprecedented in heterogeneous photocatalysis. The enhanced catalytic activity is investigated by X-ray photoelectron spectroscopy and electrochemical characterization, showing that self-assembly into supramolecular polymers increases the electron density on the active site, making the overall reaction thermodynamically more favorable. The catalyst can be recycled without loss of activity and with no change of its molecular structure as shown by pair distribution function analysis. These results demonstrate the high potential of MOP as catalysts for the photoreduction of CO 2 and open a new perspective for the electronic design of discrete molecular architectures with accessible metal sites for the production of solar fuels.

The reactivity of Cp* 4 Sb 4 (1) towards ionic compounds and transition metal complexes with labile ligands was investigated in order to synthesize polyantimony ligand complexes. The silver salts [Ag][X] and the metalate Na[Cp*Mo(CO) 3 ] were primarily used, leading in the raction with Cp* 4 Sb 4 to the formation of [Cp* 2 Sb][X] (X = TEF (2a), FAL (2b)), [(Cp*Mo(CO) 3 ) 3 (μ 3 -Sb 3 )] (3) and [Cp*Mo(CO) 2 (η 3 -Sb 3 )] (4), respectively. The reaction of 1 with the transition metal complexes [(Cp'''M) 2 (tol)] leads to a degradation of the original Sb 4 unit and to the formation of [(Cp'''M) 4 (μ 3 -Sb) 4 ] (M = Ni (5); Co (6)). Towards [Cp R Fe(CO) 2 ] 2 , substitutions on the antimony atoms were observed to give [{Cp R Fe(CO) 2 } 4 (μ 4 -Sb 4 )] (Cp R = Cp'' (7a), Cp''' (7b)). All complexes were characterized by XRD and spectroscopic methods.

Studying parallel evolution (repeated, independent evolution of similar phenotypes in similar environments) is a powerful tool to understand environment-dependent selective forces. Surface-dwelling species that repeatedly and independently colonized caves provide unique models for such studies. The primarily surface-dwelling Asellus aquaticus species complex is a good candidate to carry out such research, because it colonized several caves in Europe. By comparing 17 functional morphological traits between six cave and nine surface populations of the A. aquaticus species complex, we investigated population divergence in morphology and sexual dimorphism. We found habitat-dependent population divergence in 10 out of 17 traits, likely reflecting habitat-driven changes in selection acting on sensory systems, feeding, grooming, and antipredator mechanisms. Sexual dimorphism was present in 15 traits, explained by sexual selection acting on male traits important in male-male agonistic behavior or mate guarding and fecundity selection acting on female traits affecting offspring number and nursing. In eight traits, the degree of sexual dimorphism was habitat dependent. We conclude that cave-related morphological changes are highly trait- and function-specific and that the strength of sexual/fecundity selection strongly differs between cave and surface habitats. The considerable population variation within habitat type warrants further studies to reveal cave-specific adaptations besides the parallel patterns., Competing Interests: The authors declare no conflict of interest., (© 2021 The Authors. Ecology and Evolution published by John Wiley & Sons Ltd.)

The reactivity of the tetrahedral dipnictogen complexes [{CpMo(CO) 2 } 2 (μ,η 2 :η 2 -EE')] (E, E' = P, As, Sb, Bi; " Mo 2 EE' ") towards different one-electron oxidation agents is reported. Oxidation with [Thia][TEF] (Thia + = C 12 H 8 S 2 + ; TEF - = Al{OC(CF 3 ) 3 } 4 - ) leads to the selective formation of the radical monocations [Mo 2 EE']˙ + , which immediately dimerize to the unprecedented dicationic E 2 E' 2 ligand complexes [{CpMo(CO) 2 } 4 (μ 4 ,η 2 :η 2 :η 2 :η 2 -E'EEE')] 2+ via E-E bond formation. Single crystal X-ray diffraction revealed that, in the case of Mo 2 PAs and Mo 2 PSb , P-P bond formation occurs yielding zigzag E 2 P 2 (E = As ( 1 ), Sb ( 2 )) chains, whereas Mo 2 SbBi forms a Sb 2 Bi 2 ( 5 ) cage, Mo 2 AsSb an unprecedented As 2 Sb 2 unit representing an intermediate stage between a chain- and a cage-type structure, and Mo 2 AsBi a novel planar As 2 Bi 2 ( 4a ) cycle. Therefore, 1-5 bear the first substituent-free, dicationic hetero-E 4 ligands, stabilized by transition metal fragments. Furthermore, in the case of Mo 2 AsSb , the exchange of the counterion causes changes in the molecular structure yielding an unusual, cyclic As 2 Sb 2 ligand. The experimental results are corroborated by DFT calculations., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The synthesis of phosphines is based on white phosphorus, which is usually converted to PCl 3 , to be afterwards substituted step by step in a non-atomic efficient manner. Herein, we describe an alternative efficient transition metal-mediated process to form asymmetrically substituted phosphines directly from white phosphorus (P 4 ). Thereby, P 4 is converted to [Cp*Fe(η 5 -P 5 )] (1) (Cp* = η 5 -C 5 (CH 3 ) 5 ) in which one of the phosphorus atoms is selectively functionalized to the 1,1-diorgano-substituted complex [Cp*Fe(η 4 -P 5 R'R″)] (3). In a subsequent step, the phosphine PR'R″R‴ (R' ≠ R″ ≠ R‴ = alky, aryl) (4) is released by reacting it with a nucleophile R‴M (M = alkali metal) as racemates. The starting material 1 can be regenerated with P 4 and can be reused in multiple reaction cycles without isolation of the intermediates, and only the phosphine is distilled off., (© 2021. The Author(s).)

The functionalization of pentaphosphaferrocene [Cp*Fe(η 5 -P 5 )] ( 1 ) with cationic group 13-17 electrophiles is shown to be a general synthetic strategy towards P-E bond formation of unprecedented diversity. The products of these reactions are dinuclear [{Cp*Fe} 2 {μ,η 5:5 -(P 5 ) 2 EX 2 }][TEF] (EX 2 = BBr 2 ( 2 ), GaI 2 ( 3 ), [TEF] - = [Al{OC(CF 3 ) 3 } 4 ] - ) or mononuclear [Cp*Fe(η 5 -P 5 E)][X] (E = CH 2 Ph ( 4 ), CHPh 2 ( 5 ), SiHPh 2 ( 6 ), AsCy 2 ( 7 ), SePh ( 9 ), TeMes ( 10 ), Cl ( 11 ), Br ( 12 ), I ( 13 )) complexes of hetero-bis-pentaphosphole (( cyclo -P 5 ) 2 R) or hetero-pentaphosphole ligands ( cyclo -P 5 R), the aromatic all-phosphorus analogs of prototypical cyclopentadienes. Further, modifying the steric and electronic properties of the electrophile has a drastic impact on its reactivity and leads to the formation of [Cp*Fe(μ,η 5:2 -P 5 )SbICp'''][TEF] ( 8 ) which possesses a triple-decker-like structure. X-ray crystallographic characterization reveals the slightly twisted conformation of the cyclo -P 5 R ligands in these compounds and multinuclear NMR spectroscopy confirms their integrity in solution. DFT calculations shed light on the bonding situation of these compounds and confirm the aromatic character of the pentaphosphole ligands on a journey across the p-block., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Signal transducer and activator of transcription 3 (STAT-3) gain-of-function (GOF) syndrome is an early-onset monogenic inborn error of immunity characterized by multi-organ autoimmune disorders, growth failure and lymphoproliferation. We describe that STAT-3 GOF syndrome may be presented with hypogammaglobulinemia and recurrent severe upper and lower respiratory tract infections. In addition, the patient had lymphoproliferation, short stature and interstitial lung disease. Chest computerized tomography examinations showed mild bronchiectasis with areas of non-fibrosing alveolar-interstitial disease and maldevelopment of bilateral first ribs. Using Sanger sequencing, we revealed a novel c.508G>C, p.D170H STAT-3 variant affecting the coiled coil domain of STAT-3. Functional studies confirmed that p.D170H was a GOF variant, as shown by increased phosphorylated STAT-3 (pSTAT-3) and STAT-3 transcriptional activity. Our observation suggests that STAT-3 GOF syndrome can manifest in early childhood with hypogammaglobulinemia and recurrent severe respiratory tract infections. We suggest that patients with lymphoproliferation, hypogammaglobulinemia and severe recurrent infections should be screened for STAT-3 variants, even if autoimmune manifestations are missing., (© 2021 The Authors. Clinical & Experimental Immunology published by John Wiley & Sons Ltd on behalf of British Society for Immunology.)

The use of [Cp'' 2 Zr(η 1:1 -E 4 )] (E=P (1 a), As (1 b), Cp''=1,3-di-tert-butyl-cyclopentadienyl) as phosphorus or arsenic source, respectively, gives access to novel stable polypnictogen transition metal complexes at ambient temperatures. The reaction of 1 a/1 b with [Cp R NiBr] 2 (Cp R =Cp Bn (1,2,3,4,5-pentabenzyl-cyclopentadienyl), Cp''' (1,2,4-tri-tert-butyl-cyclopentadienyl)) was studied, to yield novel complexes depending on steric effects and stoichiometric ratios. Besides the transfer of the complete E n unit, a degradation as well as aggregation can be observed. Thus, the prismane derivatives [(Cp'''Ni) 2 (μ,η 3:3 -E 4 )] (2 a (E=P); 2 b (E=As)) or the arsenic containing cubane [(Cp'''Ni) 3 (μ 3 -As)(As 4 )] (5) are formed. Furthermore, the bromine bridged cubanes of the type [(Cp R Ni) 3 {Ni(μ-Br)}(μ 3 -E) 4 ] 2 (Cp R =Cp''': 6 a (E=P), 6 b (E=As), Cp R =Cp Bn : 8 a (E=P), 8 b (E=As)) can be isolated. Here, a stepwise transfer of E n units is possible, with a cyclo-E 4 2- ligand being introduced and unprecedented triple-decker compounds of the type [{(Cp R Ni) 3 Ni(μ 3 -E) 4 } 2 (μ,η 4:4 -E' 4 )] (Cp R =Cp Bn , Cp'''; E/E'=P, As) are obtained., (© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The reactions of the cyclo-As 5 complex [Cp*Fe(η 5 -As 5 )] (B) with the Ag I and Cu I salts of the weakly coordinating anion (WCA) [FAl{OC 6 F 10 (C 6 F 5 )} 3 ] - ([FAl] - ) are studied. These reactions allow the synthesis of the mononuclear complexes [M(η 5  : η 2 -B) 2 ][FAl] (M=Ag (1), Cu (2)) when a ratio of B/M(FAl) 2 : 1 is used. Compound 1 shows an unusual disorder of the central Ag I cation between two π-coordinating cyclo-As 5 ligands, which is absent in 2 pointing to a weak interaction of the Ag center towards the cyclo-As 5 ligands in B. When the ratio of B/Ag(FAl) is changed to 3 : 1 or 1 : 1, the respective coordination compounds [Ag(η 2 -B) 3 ][FAl] (3) and [Ag 2 (η 2  : η 2 -B) 2 ][FAl] 2 (4) are accessible. The coordination modes of the cyclo-As 5 units in 1, 3 and 4 are all different, reflecting the adaptive coordination behavior of B towards Ag I ions. The optimized geometries in the gas phase of 1-4 are determined by DFT calculations to support the bonding situation observed in their solid-state structures., (© 2021 The Authors. Published by Wiley-VCH GmbH.)

By reacting [{Cp‴Fe(CO) 2 } 2 (µ,η 1:1 -P 4 )] ( 1 ) with in situ generated phosphenium ions [Ph 2 P][A] ([A] - = [OTf] - = [O 3 SCF 3 ] - , [PF 6 ] - ), a mixture of two main products of the composition [{Cp‴Fe(CO) 2 } 2 (µ,η 1:1 -P 5 (C 6 H 5 ) 2 )][PF 6 ] ( 2a and 3a ) could be identified by extensive 31 P NMR spectroscopic studies at 193 K. Compound 3a was also characterized by X-ray diffraction analysis, showing the rarely observed bicyclo[2.1.0]pentaphosphapentane unit. At room temperature, the novel compound [{Cp‴Fe}(µ,η 4:1 -P 5 Ph 2 ){Cp‴(CO) 2 Fe}][PF 6 ] ( 4 ) is formed by decarbonylation. Reacting 1 with in situ generated diphenyl arsenium ions gives short-lived intermediates at 193 K which disproportionate at room temperature into tetraphenyldiarsine and [{Cp‴Fe(CO) 2 } 4 (µ 4 ,η 1:1:1:1 -P 8 )][OTf] 2 ( 5 ) containing a tetracyclo[3.3.0.0 2,7 .0 3,6 ]octaphosphaoctane ligand.

A synthetic pathway for the synthesis of novel anionic sandwich complexes with a cyclo-E 3 (E=P, As) ligand as an end deck was developed giving [Cp'''Co(η 3 -E 3 )] - (Cp'''=1,2,4-tri-tert-butylcyclopentadienyl, E=P ([5]), As ([6])) in good yields suitable for further reactivity studies. In the reaction with the chlorophosphanes R 2 PCl (R=Ph, Cy, t Bu), neutral complexes with a disubstituted cyclo-E 3 P (E=P, As) ligand in [Cp'''Co(η 3 -E 3 PR 2 )] (E=P (7 a-c), As (9 a-c)) were obtained. These compounds can be partially or completely converted into complexes with a cyclo-E 3 (E=P, As) ligand with an exocyclic {PR 2 } unit in [Cp'''Co(η 2 :η 1 -E 3 PR 2 )] (E=P (8 a-c), As (10 a-c)). Additionally, the insertion of the chlorosilylene [LSiCl] (L=( t BuN) 2 CPh) into the cyclo-E 3 ligand of [5] and [6] was achieved and the novel heteroatomic complexes [Cp'''Co(η 3 -E 3 SiL)] (E=P (11), As (12)) could be isolated. The reaction pathway was elucidated by DFT calculations., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)