Solid-state interconversions of coordination networks and hydrogen-bonded salts

Thermal or chemical treatment of crystalline 4,4-bipyridinium salts of [MCl4]2- (M=Co, Zn, Fe, or Pt) leads to HCl loss and formation of coordination network solids [{MCl2(4,4-bipy)}n]. For M=Co, Zn, and Fe, these solids can also be prepared by mechanochemical means. Their exposure to HCl vapor or the mechanochemical reaction of metal dichlorides with [4,4-H2bipy]Cl2 gives [4,4-H2bipy]2+ salts of [CoCl4]2-, [ZnCl4]2-, and, for the first time, [FeCl4]2-.

Novel solid networks containing Sn-H as a greener replacement for soluble alkyl Sn-H reagents in radical assisted organic synthesis

DiGrignard reagents of the form XMg(CH2)(n)MgX, where X = Br or I and n = 6, 8, 10 or 12, were allowed to react with PhSnCl3 to produce highly cross-linked Ph-Sn polymeric networks. The Sn-H moiety was incorporated into these insoluble network polymers by treatment with Br-2 and NaBH4. Excellent accessibility of the Sn-H was displayed by these solvent penetrable but insoluble networks, giving them higher Sn-H loadings than all previously reported supported reagents. These reagents were totally regenerable in NaBH4 for radical assisted organic synthesis and no detectable leaching of the Sn into solution was observed during these reactions.

Syntheses of two new 1D and 3D networks of Cu(II) and Co(II) using malonate and urotropine as bridging ligands: Crystal structures and magnetic studies

Two new metal-organic based polymeric complexes, [Cu-4(O2CCH2CO2)(4)(L)].7H(2)O (1) and [CO2(O2CCH2CO2)(2)(L)].2H(2)O (2) [L = hexamethylenetetramine (urotropine)], have been synthesized and characterized by X-ray crystal structure determination and magnetic studies. Complex 1 is a 1D coordination polymer comprising a carboxylato, bridged Cu-4 moiety linked by a tetradentate bridging urotropine. Complex 2 is a 3D coordination polymer made of pseudo-two-dimensional layers of Co(II) ions linked by malonate anions in syn-anticonformation which are bridged by bidentate urotropine in trans fashion, Complex 1 crystallizes in the orthothombic system, space group Pmmn, with a = 14,80(2) Angstrom, b = 14.54(2) Angstrom, c = 7.325(10) Angstrom, beta = 90degrees, and Z = 4. Complex 2 crystallizes in the orthorhombic system, space group Imm2, a = 7.584(11) Angstrom, b = 15.80(2) Angstrom, c = 6.939(13) Angstrom, beta = 90.10degrees(1), and Z = 4. Variable temperature (300-2 K) magnetic behavior reveals the existence of ferro- and antiferromagnetic interactions in 1 and only antiferromagnetic interactions in 2. The best fitted parameters for complex 1 are J = 13.5 cm(-1), J = -18.1 cm(-1), and g = 2.14 considering only intra-Cu-4 interactions through carboxylate and urotropine pathways. In case of complex 2, the fit of the magnetic data considering intralayer interaction through carboxylate pathway as well as interlayer interaction via urotropine pathway gave no satisfactory result at this moment using any model known due to considerable orbital contribution of Co(II) ions to the magnetic moment and its complicated structure. Assuming isolated Co(II) ions (without any coupling, J = 0) the shape of the chi(M)T curve fits well with experimental data except at very low temperatures.

Syntheses, crystal structures and magnetic properties of carboxylato-bridged polymeric networks of Mn-II

Three new carboxylato-bridged polymeric networks of Mn-II having molecular formula [Mn(ox)(dpyo)](n) (1), {[Mn-2(mal)(2)(bpee)(H2O)(2)]center dot 0.5(bpee)center dot 0.5(CH3OH)}n, (2) and {[Mn-3(btc)(2)(2,2'-bipy)(2)(H2O)(6)]center dot 4H(2)O}(n) (3) [dpyo, 4,4'-bipyridine N,N'dioxide; bpee, trans-1,2 bis(4-pyridyl) ethylene; 2,2'-bipy, 2,2'-bipyridine; ox = oxalate dianion; mal = malonate dianion; btc = 1,3,5-benzenetricarboxylate trianion] have been synthesized and characterized by single-crystal X-ray diffraction studies and low temperature magnetic measurements. Structure determination of complex I reveals a covalent bonded 2D network containing bischelating oxalate and bridging dpyo; complex 2 is a covalent,bonded 3D polymeric architecture, formed by bridging malonate and bpee ligands, resulting in an open framework with channels filled by uncoordinated disordered bpee and methanol molecules. Whereas complex 3, comprising btc anions bound to three metal centers, is a 1D chain which further extends its dimensionality to 3D via pi-pi and H-bonding interactions. Low temperature magnetic measurements reveal the existence of weak antiferromagnetic interaction in all these complexes. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006).

New copper(I) cyanide networks: interpenetration, self-penetration and polymorphism

The structures Of four alkali-metal copper (I) cyanides, KCu2(CN)(3)(H2O)-H-.-II (I), K2Cu3(CN)(5) (II), CsCu3(CN)(4) (III) and KCu3(CN)(4) (IV) are described. Three of these, ((II)-(IV)), with previously unknown ACN:CuCN ratios have new copper-cyanide frameworks, whilst (1) is a new polymorph of KCu2(CN)(3)(H2O)-H-.. These structures are discussed in terms of assembly from the simple building units Cu(CN)(2/2), Cu(CN)(3/2), Cu(CN)(2/2)(CN)(1/1) and Cu(CN)(4/2). Compounds (I), (II) and (III) are layered materials based on (6,3) nets containing (CuCN)(6) rings (I) and (CuCN)(8) rings (II) and (III). In compound (IV), (4,4) nets containing (CuCN)(12) rings link to generate a three-dimensional network. Both (III) and (IV) are examples of interpenetrating solids in which two and four identical networks interweave, respectively. These materials illustrate the structural versatility of copper (I) in cyanide frameworks. (c) 2006 Elsevier SAS. All rights reserved.

Informal communication networks and the diffusion of innovations in UK construction projects: A research design

The UK industry has been criticised for being slow to adopt construction process innovations. Research shows that the idiosyncrasies of participants, their roles in the system and the contextual differences between sections of the industry make this a highly complex problem. There is considerable evidence that informal social networks play a key role in diffusion of innovations. The aim is to identify informal communication networks of project participants and the role these play in the diffusion of construction innovations. The characteristics of this network will be analysed in order to understand how they can be used to accelerate innovation diffusion within and between projects. Social Network Analysis is used to determine informal communication routes. Control and experiment case study projects are used within two different organizations. This allows informal communication routes concerning innovations to be mapped, whilst testing if the informal routes can facilitate diffusion. Analysis will focus upon understanding the combination of informal strong and weak ties, and how these impede or facilitate the diffusion of the innovation. Initial work suggests the presence of an informal communication network. Actors within this informal network, and the organization's management are unaware of its' existence and their informal roles within it. Thus, the network remains an untapped medium regarding innovation diffusion. It is proposed that successful innovation diffusion is dependent upon understanding informal strong and weak ties, at project, organization and industry level.

Technology sourcing, knowledge management and governance in international inter-organizational innovation networks

This conceptual paper aims to improve our understanding of how internationalised firms use outsourcing and offshoring strategies to manage knowledge and information through the life-cycle of integrated product-service solutions. More precisely, we identify the appropriate theoretical framework for this analysis and investigate through in-depth case studies how UK engineering firms organise, coordinate, and incentivise work that is executed in globally distributed teams. Our research focuses on their UK and India offices to study the organisation and governance of distributed teams. The research has several theoretical dimensions - organization; geography; time and knowledge - that it addresses as boundary challenges.

Teachers' networks in and out of school

A 'mapping task' was used to explore the networks available to head teachers, school coordinators and local authority staff. Beginning from an ego-centred perspective on networks, we illustrate a number of key analytic categories, including brokerage, formality, and strength and weakness of links with reference to a single UK primary school. We describe how teachers differentiate between the strength of network links and their value, which is characteristically related to their potential impact on classroom practice.

Simulating global properties of electroencephalograms with minimal random neural networks

The human electroencephalogram (EEG) is globally characterized by a 1/f power spectrum superimposed with certain peaks, whereby the "alpha peak" in a frequency range of 8-14 Hz is the most prominent one for relaxed states of wakefulness. We present simulations of a minimal dynamical network model of leaky integrator neurons attached to the nodes of an evolving directed and weighted random graph (an Erdos-Renyi graph). We derive a model of the dendritic field potential (DFP) for the neurons leading to a simulated EEG that describes the global activity of the network. Depending on the network size, we find an oscillatory transition of the simulated EEG when the network reaches a critical connectivity. This transition, indicated by a suitably defined order parameter, is reflected by a sudden change of the network's topology when super-cycles are formed from merging isolated loops. After the oscillatory transition, the power spectra of simulated EEG time series exhibit a 1/f continuum superimposed with certain peaks. (c) 2007 Elsevier B.V. All rights reserved.

Stability criteria for the contextual emergence of macrostates in neural networks

More than thirty years ago, Amari and colleagues proposed a statistical framework for identifying structurally stable macrostates of neural networks from observations of their microstates. We compare their stochastic stability criterion with a deterministic stability criterion based on the ergodic theory of dynamical systems, recently proposed for the scheme of contextual emergence and applied to particular inter-level relations in neuroscience. Stochastic and deterministic stability criteria for macrostates rely on macro-level contexts, which make them sensitive to differences between different macro-levels.