Simultaneous bridge-localized and mixed-valence character in diruthenium radical cations featuring diethynylaromatic bridging ligands

A series of bimetallic ruthenium complexes [{Ru(dppe)Cp*}2(μ-C≡CArC≡C)] featuring diethynylaromatic bridging ligands (Ar = 1,4-phenylene, 1,4-naphthylene, 9,10-anthrylene) have been prepared and some representative molecular structures determined. A combination of UV–vis–NIR and IR spectroelectrochemical methods and density functional theory (DFT) have been used to demonstrate that one-electron oxidation of compounds [{Ru(dppe)Cp*}2(μ-C≡CArC≡C)](HC≡CArC≡CH = 1,4-diethynylbenzene; 1,4-diethynyl-2,5-dimethoxybenzene; 1,4-diethynylnaphthalene; 9,10-diethynylanthracene) yields solutions containing radical cations that exhibit characteristics of both oxidation of the diethynylaromatic portion of the bridge, and a mixed-valence state. The simultaneous population of bridge-oxidized and mixed-valence states is likely related to a number of factors, including orientation of the plane of the aromatic portion of the bridging ligand with respect to the metal d-orbitals of appropriate π-symmetry.

Bridging a yawning chasm: EEG investigations into the debate concerning the role of the human mirror neuron system in contagious yawning

Ongoing debate in the literature concerns whether there is a link between contagious yawning and the human mirror neuron system (hMNS). One way of examining this issue is with the use of the electroencephalogram (EEG) to measure changes in mu activation during the observation of yawns. Mu oscillations are seen in the alpha bandwidth of the EEG (8–12 Hz) over sensorimotor areas. Previous work has shown that mu suppression is a useful index of hMNS activation and is sensitive to individual differences in empathy. In two experiments, we presented participants with videos of either people yawning or control stimuli. We found greater mu suppression for yawns than for controls over right motor and premotor areas, particularly for those scoring higher on traits of empathy. In a third experiment, auditory recordings of yawns were compared against electronically scrambled versions of the same yawns. We observed greater mu suppression for yawns than for the controls over right lateral premotor areas. Again, these findings were driven by those scoring highly on empathy. The results from these experiments support the notion that the hMNS is involved in contagious yawning, emphasise the link between contagious yawning and empathy, and stress the importance of good control stimuli.

Bridging the Faraoni and Selli oceanic anoxic events: late Hauterivian to early Aptian dysaerobic to anaerobic phases in the Tethys.

A detailed geochemical analysis was performed on the upper part of the Maiolica Formation in the Breggia (southern Switzerland) and Capriolo sections (northern Italy). The analysed sediments consist of well-bedded, partly siliceous, pelagic carbonate, which lodges numerous thin, dark and organic-rich layers. Stable-isotope, phosphorus, organic-carbon and a suite of redox-sensitive trace-element contents (RSTE: Mo, U, Co, V and As) were measured. The RSTE pattern and Corg:Ptot ratios indicate that most organic-rich layers were deposited under dysaerobic rather than anaerobic conditions and that latter conditions were likely restricted to short intervals in the latest Hauterivian, the early Barremian and the pre-Selli early Aptian. Correlations are both possible with organic-rich intervals in central Italy (the Gorgo a Cerbara section) and the Boreal Lower Saxony Basin, as well as with the facies and drowning pattern in the Helvetic segment of the northern Tethyan carbonate platform. Our data and correlations suggest that the latest Hauterivian witnessed the progressive installation of dysaerobic conditions in the Tethys, which went along with the onset in sediment condensation, phosphogenesis and platform drowning on the northern Tethyan margin, and which culminated in the Faraoni anoxic episode. This episode is followed by further episodes of dysaerobic conditions in the Tethys and the Lower Saxony Basin, which became more frequent and progressively stronger in the late early Barremian. Platform drowning persisted and did not halt before the latest early Barremian. The late Barremian witnessed diminishing frequencies and intensities in dysaerobic conditions, which went along with the progressive installation of the Urgonian carbonate platform. Near the Barremian-Aptian boundary, the increasing density in dysaerobic episodes in the Tethyan and Lower Saxony Basins is paralleled by a change towards heterozoan carbonate production on the northern Tethyan shelf. The following return to more oxygenated conditions is correlated with the second phase of Urgonian platform growth and the period immediately preceding and corresponding to the Selli anoxic episode is characterised by renewed platform drowning and the change to heterozoan carbonate production. Changes towards more humid climate conditions were the likely cause for the repetitive installation of dys- to anaerobic conditions in the Tethyan and Boreal basins and the accompanying changes in the evolution of the carbonate platform towards heterozoan carbonate-producing ecosystems and platform drowning.

1,1′-Bis(diphenylphosphino)ferrocene bridging two mono(cyclopentadienyl) cobalt moieties: synthesis, structure, electrochemistry and DFT studies

Reaction of [Co(eta(5)-C5H5)(CO)(2)], 1, with 1,1'-bis(diphenylphosphino)ferrocene (dppf) yields the new trinuclear complex [Co(eta(5)-C5H5)(CO)](2)(mu-dppf), 2, which was structurally characterised by single crystal X-ray diffraction and showed two Co(eta(5)-C5H5)(CO) moieties covalently linked by a dppf bridge. Electrochemical studies in dichloromethane revealed that both Co(I) and Fe(II) in the precursors were oxidized to Co(II)/Co(III) and Fe(III), respectively. On the other hand, in 2 the two first oxidation waves were assigned to Co, the Fe(II) centre requiring a higher potential than in free dppf. DFT calculations showed that the HOMOs of 2 were localised in the Co fragments, owing to the destabilisation of the Co(eta(5)-C5H5)(CO) orbitals after binding dppf.

Synthesis and crystal structures of μ-oxido- and μ-hydroxido-bridged dinuclear iron(III) complexes with an N2O donor ligand - a theoretical study on the influence of weak forces on the Fe-O-Fe bridging angle

The synthesis and crystal structures of three nonheme di-iron(III) complexes with a tridentate N,N,O Schiff-base ligand, 2-({[2-(dimethylamino) ethyl] imino} methyl) phenol (HL), are reported. Complexes [Fe2OL2(NCO)(2)] (1a) and [Fe2OL2(SAL)(2)]center dot H2O [SAL = o-(CHO)C6H4O-] (1b) are unsupported mu-oxido-bridged dimers, and [Fe-2(OH)L-2(HCOO)(2)-(Cl)] (2) is a mu-hydroxido-bridged dimer supported by a formato bridging ligand. All complexes have been characterized by X-ray crystallography and spectroscopic analysis. Complex 1b has been reported previously; however, it has been reinvestigated to confirm the presence of a crucial water molecule in the solid state. Structural analyses show that in 1a the iron atoms are pentacoordinate with a bent Fe-O-Fe angle [142.7(2)degrees], whereas in 2 the metal centers are hexacoordinate with a normal Fe-OH-Fe bridging angle [137.9(2)degrees]. The Fe-O-Fe angles in complexes 1a and 1b differ significantly to those usually shown by (mu-oxido) Fe-III complexes. A theoretical study has been performed in order to rationalize this deviation. Moreover, the influence of the water molecule observed in the solid-state structure of 1b on the Fe-O-Fe angle is also analyzed theoretically.

Creative participation in construction firms: bridging creativity and innovation

An intricate evolution of mainstream theories follows the growing need to explain employees’ commitment and engagement. Our understanding of these work-related phenomena and behaviour has improved but creativity and innovation as desired indicators are still often treated as coexisting constructs with very little attention given to a state of willingness of an individual to even consider contributing ideas. In this research we investigate the influence of knowledge and understanding, perceived radicality, personality dimensions, and favouring of ideas on employee willingness to creatively participate in order to trace its existence in propagation of ideas. A total of 76 construction and non-construction professionals participated in between-subject quasi-experiments. We also proposed IPO-based radicality of ideas construct from the viewpoint of employees involved in the processes of transformation. The research findings show that experts with deep understanding of the work are more likely to contribute highly radical ideas to decision-makers than less knowledgeable employees. Furthermore, personal factors that impact employee willingness to creatively participate have been valued higher than organisational factors. Personality dimensions by The BigFive Inventory have shown no effect on willingness to contribute ideas, while favouring of ideas showed a significant effect. In general, the findings show similarities with some studies of consumer willingness to participate in co-creation processes and thus indicate that firms may be studied as dynamic internal markets of ideas.

Structural and magnetic studies of Schiff base complexes of nickel(ii) nitrite: change in crystalline state, ligand rearrangement and a very rare μ-nitrito-1κO:2κN:3κO′ bridging mode

Four new nickel(II) complexes, [Ni2L2(NO2)2]·CH2Cl2·C2H5OH, 2H2O (1), [Ni2L2(DMF)2(m-NO2)]ClO4·DMF (2a), [Ni2L2(DMF)2(m-NO2)]ClO4 (2b) and [Ni3L¢2(m3-NO2)2(CH2Cl2)]n·1.5H2O (3) where HL = 2-[(3-amino-propylimino)-methyl]-phenol, H2L¢ = 2-({3-[(2-hydroxy-benzylidene)-amino]-propylimino}-methyl)-phenol and DMF = N,N-dimethylformamide, have been synthesized starting with the precursor complex [NiL2]·2H2O, nickel(II) perchlorate and sodium nitrite and characterized structurally and magnetically. The structural analyses reveal that in all the complexes, NiII ions possess a distorted octahedral geometry. Complex 1 is a dinuclear di-m2-phenoxo bridged species in which nitrite ion acts as chelating co-ligand. Complexes 2a and 2b also consist of dinuclear entities, but in these two compounds a cis-(m-nitrito-1kO:2kN) bridge is present in addition to the di-m2-phenoxo bridge. The molecular structures of 2a and 2b are equivalent; they differ only in that 2a contains an additional solvated DMF molecule. Complex 3 is formed by ligand rearrangement and is a one-dimensional polymer in which double phenoxo as well as m-nitrito-1kO:2kN bridged trinuclear units are linked through a very rare m3-nitrito-1kO:2kN:3kO¢ bridge. Analysis of variable-temperature magnetic susceptibility data indicates that there is a global weak antiferromagnetic interaction between the nickel(II) ions in four complexes, with exchange parameters J of -5.26, -11.45, -10.66 and -5.99 cm-1 for 1, 2a, 2b and 3, respectively

Bridging the gap between research and practice in organizational network analysis: a conversation between Rob Cross and Martin Kilduff

The article features a conversation between Rob Cross and Martin Kilduff about organizational network analysis in research and practice. It demonstrates the value of using social network perspectives in HRM. Drawing on the discussion about managing personal networks; managing the networks of others; the impact of social networking sites on perceptions of relationships; and ethical issues in organizational network analysis, we propose specific suggestions to bring social network perspectives closer to HRM researchers and practitioners and rebalance our attention to people and to their relationships.

'Nature Conservation': a new dimension in Open Access publishing bridging science and application

This Editorial presents the focus, scope and policies of the inaugural issue of Nature Conservation, a new open access, peer-reviewed journal bridging natural sciences, social sciences and hands-on applications in conservation management. The journal covers all aspects of nature conservation and aims particularly at facilitating better interaction between scientists and practitioners. The journal will impose no restrictions on manuscript size or the use of colour. We will use an XML-based editorial workflow and several cutting-edge innovations in publishing and information dissemination. These include semantic mark-up of, and enhancements to published text, data, and extensive cross-linking within the journal and to external sources. We believe the journal will make an important contribution to better linking science and practice, offers rapid, peer-reviewed and flexible publication for authors and unrestricted access to content.

Social development: bridging the theory-practice divide, past and present

Introduces a collection of articles appearing in a special issue that reflect on social development, considering the various intellectual forms social development has taken, how development thinking has been shaped by different concepts in different periods, and how contributors' personal experiences with social development research has been applied to social development practice.

Bridging the segmentation theory/practice divide

More than thirty years ago, Wind's seminal review of research in market segmentation culminated with a research agenda for the subject area. In the intervening period, research has focused on the development of segmentation bases and models, segmentation research techniques and the identification of statistically sound solutions. Practical questions about implementation and the integration of segmentation into marketing strategy have received less attention, even though practitioners are known to struggle with the actual practice of segmentation. This special issue is motivated by this tension between theory and practice, which has shaped and continues to influence the research priorities for the field. Although many years may have elapsed since Wind's original research agenda, pressing questions about effectiveness and productivity apparently remain; namely: (i) concerns about the link between segmentation and performance, and its measurement; and (ii) the notion that productivity improvements arising from segmentation are only achievable if the segmentation process is effectively implemented. There were central themes to the call for papers for this special issue, which aims to develop our understanding of segmentation value, productivity and strategies, and managerial issues and implementation.

Talent management and expatriation: bridging two streams of research and practice

This paper argues that talent management and expatriation are two significantly overlapping but separate areas of research and that bringing the two together has significant and useful implications for both research and practice. We offer indications of how this bringing together might work, in particular developing the different results that will come from narrower and broader concepts of talent management. Our framework defines global talent management as a combination of high-potential development and global careers development. The goal of the paper is to lay the foundations for future research while encouraging organizations to manage expatriation strategically in a talent-management perspective.

Auto ID-Bridging the physical and the digital on construction projects

This book looks at how auto-ID has evolved and how it can be used in the construction industry and across projects from the perspective of all the stakeholders, from owners to design consultants, contractors and the supply chain. It could help to improve efficiency, reduce costs, ensure quality, protect the environment, and enhance safety.

Diruthenium complexes with bridging diethynyl polyaromatic ligands: synthesis, spectroelectrochemistry, and theoretical calculations

This work describes syntheses and electrochemical, spectroscopic, and bonding properties in a new series of dinuclear ruthenium(II) complexes bridged by polyaromatic (biphenyl, fluorene, phenanthrene, and pyrene) alkynyl ligands. Longitudinal expansion of the π-conjugated polyaromatic core of the bridging ligands caused a reduced potential difference between the anodic steps and reinforced their bridge-localized nature, as evidenced by UV/vis/near-IR and IR spectroelectrochemical data combined with DFT and TDDFT calculations. Importantly, the intricate multiple IR ν(CC) absorption bands for the singly oxidized states imply a thermal population of a range of conformers (rotamers) with distinct electronic character. This behavior was demonstrated with more accurate DFT calculations of selected nontruncated 1e− oxidized complexes in three different conformations. The combined experimental and theoretical data reveal that thermally populated rotamers featuring various mutual orientations of the ligated metal termini and the bridging diethynyl polyaromatic moieties have a significant impact on the electronic absorption and ν(CC) wavenumbers of the singly oxidized systems.

New metallomolecular wires based on carbon-rich bridging systems: a systematic study

This dissertation presents and discusses the preparation of molecular wires (MW) candidates that would then be probed for electron transfer properties. These wires are bridged by 1,4-diethynylbenzene derivatives with alkoxy side chains with palladium and ruthenium metal complex termini. Characterization of these compounds was performed by usual spectroscopic techniques like 1H, 13C{1H} and 31P{1H} NMR, MS, FTIR and UV-Vis as well as by cyclic voltammetry which allowed classifying the candidates in the Robin–Day system and determination of bridges side chain and length effects on electronic transport. Preparation of the 1,4-diethynylbenzene derivatives was done with synthetic pathways that relied heavily in palladium catalyzed cross-couplings (Sonogashira). A family of single ringed 1,4-diethynylbenzene ligands with different length alkoxy side chains (OCH3, OC2H5, OC7H15) was thus prepared allowing for the influence of these ring decorations to be assessed. The ruthenium binuclear rods showed communication between metal centres only when the shorter ligands were used whereas the longer Ru complexes showed only one redox pair in CV studies which is in agreement to non-communicating metal centres. Cyclic voltammetry studies show irreversible one wave processes for palladium dinuclear complexes, making these rods function as molecular insulators. Fluorescence decay studies performed on the prepared compounds (ligands and complexes) show a pattern of decreasing decay times upon coordination to the metal centres which can due to ligand charge redistribution upon coordination leading to non-radiative relaxation paths. Regarding the X-ray structures, two new ligand related structures were obtained as well as new structure for a palladium rod. The effect of the side chains was observed to be important to the wires’ electronic properties when comparing with the analogues without a side chain. The effect brought by longer chains is nevertheless almost negligible.