Use of a reduced Schiff-Base ligand to prepare novel chloro-bridged chains of rare Cu(II) trinuclear complexes with mixed azido/oxo and chloro/oxo bridges

Two mixed bridged one-dimensional (1D) polynuclear complexes, [Cu3L2(mu(1,1)-N-3)(2)(mu-Cl)Cl](n) (1) and {[Cu3L2(mu-Cl)(3)Cl]center dot 0.46CH(3)OH}(n), (2), have been synthesized using the tridentate reduced Schiff-base ligand HL (2-[(2-dimethylamino-ethylamino)-methyl]-phenol). The complexes have been characterized by X-ray structural analyses and variable-temperature magnetic susceptibility measurements. In both complexes the basic trinuclear angular units are joined together by weak chloro bridges to form a 1D chain. The trinuclear structure of 1 is composed of two terminal square planar [Cu(L)(mu(1,1)-N-3)] units connected by a central Cu(II) atom through bridging nitrogen atoms of end-on azido ligands and the phenoxo oxygen atom of the tridentate ligand. These four coordinating atoms along with a chloride ion form a distorted trigonal bipyramidal geometry around the central Cu(II). The structure of 2 is similar; the only difference being a Cl bridge replacing the mu(1,1)-N-3 bridge in the trinuclear unit. The magnetic properties of both trinuclear complexes can be very well reproduced with a simple linear symmetrical trimer model (H = JS(i)S(i+1)) with only one intracluster exchange coupling (J) including a weak intertrimer interaction (.j) reproduced with the molecular field approximation. This model provides very satisfactory fits for both complexes in the whole temperature range with the following parameters: g = 2.136(3), J = 93.9(3) cm(-1) and zj= -0.90(3) cm(-1) (z = 2) for 1 and g = 2.073(7), J = -44.9(4) cm(-1) and zJ = -1.26(6) cm(-1) (z = 2) for 2.

Synthesis, crystal structure and magnetic properties of three unprecedented tri-nuclear and one very rare tetra-nuclear copper(II) Schiff-base complexes supported by mixed azido/phenoxo/nitrato or acetato bridges

Three novel mixed bridged trinuclear and one tetranuclear copper(II) complexes of tridentate NNO donor Schiff base ligands [Cu-3(L-1)(2)(mu(LI)-N-3)(2)(CH3OH)(2)(BF2)(2)] (1), [Cu-3(L-1)(2)(mu(LI)-NO3-I kappa O.2 kappa O')(2)] (2), [Cu-3(L-2)(2)(mu(LI)-N-3)(2)(mu-NOI-I kappa O 2 kappa O')(2)] (3) and [Cu-4(L-3)(2)(mu(LI)-N-3)(4)(mu-CH3COO-I kappa O 2 kappa O')(2)] (4) have been synthesized by reaction of the respective tridentate ligands (L-1 = 2[1-(2-dimethylamino-ethylimino)-ethyl]-phenol, L-2 = 2[1-(2-diethylamino-ethylimino)-ethyl]-phenol, L-3 = 2-[1-(2-dimethylamino-ethylimino)-methyl]-phenol) with the corresponding copper(II) salts in the presence of NaN3 The complexes are characterized by single-crystal X-ray diffraction analyses and variable-temperature magnetic measurements Complex 1 is composed of two terminal [Cu(L-1)(mu(LI)-N-3)] units connected by a central [Cu(BF4)(2)] unit through nitrogen atoms of end-on azido ligands and a phenoxo oxygen atom of the tridentate ligand The structures of 2 and 3 are very similar, the only difference is that the central unit is [Cu(NO1)(2)] and the nitrate group forms an additional mu-NO3-I kappa O 2 kappa O' bridge between the terminal and central copper atoms In complex 4, the central unit is a di-mu(L1)-N-3 bridged dicopper entity, [Cu-2(mu(L1)-N-3)(2)(CH3COO)(2)] that connects two terminal [Cu(L-3)(mu(L1)-N-3)] units through end-on azido; phenoxo oxygen and mu-CH3COO-1 kappa O center dot 2 kappa O' triple bridges to result in a tetranuclear unit Analyses of variable-temperature magnetic susceptibility data indicates that there is a global weak antiferromagnetic interaction between the copper(II) ions in complexes 1-3, with the exchange parameter J of -9 86, -11 6 and -19 98 cm(-1) for 1-3, respectively In complex 4 theoretical calculations show the presence of an antiferromagnetic coupling in the triple bridging ligands (acetato, phenoxo and azido) while the interaction through the double end-on azido bridging ligand is strongly ferromagnetic.

Magnetic coupling in trinuclear partial cubane copper(II) complexes with a hydroxo bridging core and peripheral phenoxo bridges from NNO donor Schiff base ligands

Three new trinuclear copper(II) complexes, [(CuL1)(3)(mu(3)-OH)](ClO4)(2)center dot 3.75H(2)O (1), [(CuL2)(3)(mu(3)-OH)](ClO4)(2) (2) and [(CuL3)(3)(mu(3)-OH)](BF4)(2)center dot 0.5CH(3)CN (3) have been synthesized from three tridentate Schiff bases HL1, HL2, and HL3 (HL1 = 2-[(2-amino-ethylimino)-methyl]-phenol, HL2 = 2-[(2-methylamino-ethylimino)-methyl]-phenol and HL3 = 2-[1-(2-dimethylamino-ethylimino)-ethyl]-phenol). The complexes are characterized by single-crystal X-ray diffraction analyses, IR, UV-vis and EPR spectroscopy, and variable-temperature magnetic measurements. All the compounds contain a partial cubane [Cu3O4] core consisting of the trinuclear unit [(CuL)(3)(mu(3)-OH)](2+) together with perchlorate or fluoroborate anions. In each of the complexes, the three copper atoms are five-coordinated with a distorted square-pyramidal geometry except in complex 1, in which one of the Cu-II ions of the trinuclear unit is six-coordinate being in addition weakly coordinated to one of the perchlorate anions. Variable-temperature magnetic measurements and EPR spectra indicate an antiferromagnetic exchange coupling between the CuII ions of complexes 1 and 2, while this turned out to be ferromagnetic for complex 3. Experimental values have been fitted according to an isotropic exchange Hamiltonian. Calculations based on Density Functional Theory have also been performed in order to estimate the exchange coupling constants in these three complexes. Both sets of values indicate similar trends and specially calculated J values establish a magneto-structural correlation between them and the Cu-O-Cu bond angle, in that the coupling is more ferromagnetic for smaller bond angle values.

Grey-box radial basis function modelling

A fundamental principle in data modelling is to incorporate available a priori information regarding the underlying data generating mechanism into the modelling process. We adopt this principle and consider grey-box radial basis function (RBF) modelling capable of incorporating prior knowledge. Specifically, we show how to explicitly incorporate the two types of prior knowledge: (i) the underlying data generating mechanism exhibits known symmetric property, and (ii) the underlying process obeys a set of given boundary value constraints. The class of efficient orthogonal least squares regression algorithms can readily be applied without any modification to construct parsimonious grey-box RBF models with enhanced generalisation capability.

A new tetranuclear copper(II) complex with oximate bridges: structure, magnetic properties and DFT study

A new tetranuclear complex, [Cu4L4](ClO4)4·2H2O (1), has been synthesized from the self-assembly of copper(II) perchlorate and the tridentate Schiff base ligand (2E,3E)-3-(2-aminopropylimino) butan-2-one oxime (HL). Single-crystal X-ray diffraction studies reveal that complex 1 consists of a Cu4(NO)4 core where the four copper(II) centers having square pyramidal environment are arranged in a distorted tetrahedral geometry. They are linked together by a rare bridging mode (μ3-η1,η2,η1) of oximato ligands. Analysis of magnetic susceptibility data indicates moderate antiferromagnetic (J1 = −48 cm−1, J2 = −40 cm−1 and J3 = −52 cm−1) exchange interaction through σ-superexchange pathways (in-plane bridging) of the oxime group. Theoretical calculations based on DFT technique have been used to obtain the energy states of different spin configurations and estimate the coupling constants and to understand the exact magnetic exchange pathways.

Boundaries and Bridges: the influence of James Cooksey Culwick on the development of the teaching and learning of music in nineteenth century Ireland

James Cooksey Culwick (1845-1907) was born in England. Trained as chorister and organist in Lichfield Cathedral, he moved to Ireland at twenty- one and remained until his death in 1907. Although his reputation as scholar, musician and teacher was acknowledged widely during his lifetime - he received an honorary doctorate from University of Dublin (1893) - little is known about the contribution he made to music education. This paper addresses this gap in the literature and argues that it was Culwick's singular achievement to pay attention to music pedagogy at secondary level, by recognizing that music could be seen as a serious career option for girls, and by providing resources for teachers which emphasised the development of an 'art-feeling' in pupils of all abilities. In addition, he considered Irish music as an art which had significance as music first, and Irish music second, and advocated a 'laudable tolerance' for opposing views on matters of cultural identity to Ireland at the end of the nineteenth century.

Thinking out of the box – skills for work

Since the Dearing Report .1 there has been an increased emphasis on the development of employability and transferable (‘soft’) skills in undergraduate programmes. Within STEM subject areas, recent reports concluded that universities should offer ‘greater and more sustainable variety in modes of study to meet the changing demands of industry and students’.2 At the same time, higher education (HE) institutions are increasingly conscious of the sensitivity of league table positions on employment statistics and graduate destinations. Modules that are either credit or non-credit bearing are finding their way into the core curriculum at HE. While the UK government and other educational bodies argue the way forward over A-level reform, universities must also meet the needs of their first year cohorts in terms of the secondary to tertiary transition and developing independence in learning.

Inside the black box: unravelling the development viability appraisal process

Over the last decade issues related to the financial viability of development have become increasingly important to the English planning system. As part of a wider shift towards the compartmentalisation of planning tasks, expert consultants are required to quantify, in an attempt to rationalise, planning decisions in terms of economic ‘viability’. Often with a particular focus on planning obligations, the results of development viability modelling have emerged as a key part of the evidence base used in site-specific negotiations and in planning policy formation. Focussing on the role of clients and other stakeholders, this paper investigates how development viability is tested in practice. It draws together literature on the role of calculative practices in policy formation, client feedback and influence in real estate appraisals and stakeholder engagement and consultation in the planning literature to critically evaluate the role of clients and other interest groups in influencing the production and use of development viability appraisal models. The paper draws upon semi-structured interviews with the main producers of development viability appraisals to conclude that, whilst appraisals have the potential to be biased by client and stakeholder interests, there are important controlling influences on potential opportunistic behaviour. One such control is local authorities’ weak understanding of development viability appraisal techniques which limits their capacity to question the outputs of appraisal models. However, this also is of concern given that viability is now a central feature of the town planning system.

An experiment on energy-saving competition with socially responsible consumers: opening the black box

We present results from experimental price-setting oligopolies in which green firms undertake different levels of energy-saving investments motivated by public subsidies and demand-side advantages. We find that consumers reveal higher willingness to pay for greener sellers’ products. This observation in conjunction to the fact that greener sellers set higher prices is compatible with the use and interpretation of energy-saving behaviour as a differentiation strategy. However, sellers do not exploit the resulting advantage through sufficiently high price-cost margins, because they seem trapped into “run to stay still” competition. Regarding the use of public subsidies to energy-saving sellers we uncover an undesirable crowding-out effect of consumers’ intrinsic tendency to support green manufacturers. Namely, consumers may be less willing to support a green seller whose energy-saving strategy yields a direct financial benefit. Finally, we disentangle two alternative motivations for consumer’s attractions to pro-social firms; first, the self-interested recognition of the firm’s contribution to the public and private welfare and, second, the need to compensate a firm for the cost entailed in each pro-social action. Our results show the prevalence of the former over the latter.