Synthesis of hexa-peri-hexabenzocoronenes - from building blocks to functional materials

Discotic hexa-peri-hexabenzocoronene (HBC) derivatives have attracted intensive scientific interest due to their unique optoelectronic properties, which depends, to a large extend, upon the attached functional groups. The presented work covers the synthesis of novel HBC building blocks and new HBC derivatives as functional materials. The traditional preparation of HBC derivatives requires elaborate synthetic techniques and tremendous effort. Especially, more than 10 synthetic steps are usually necessary to approach HBCs with lower symmetries. In order to simplify the synthetic work and reduce the high costs, a novel synthetic strategy involving only four steps was developed based on 2,3,5,6-tetraphenyl-1,4-diiodobenzene intermediates and palladium catalyzed Suzuki cross coupling reactions. In order to introduce various functionalities and expand the diversity of multi-functionalizations, a novel C2v-symmetric dihalo HBC building block 2-47, which contains one iodine and one bromine in para positions, was prepared following the traditional intermolecular [4+2] Diels-Alder reaction route. The outstanding chemical selectivity between iodo and bromo groups in this compound consequently leads to lots of HBC derivatives bearing different functionalities. Directly attached heteroatoms will improve the material properties. According to the application of intramolecular Scholl reaction to a para-dimethoxy HPB, which leads to a meta-dimethoxy HBC, a phenomenon of phenyl group migration was discovered. Thereby, several interesting mechanistic details involving arenium cation intermediates were discussed. With a series of dipole functionalized HBCs, the molecular dynamics of this kind of materials was studied in different phases by DSC, 2D WAXD, solid state NMR and dielectric spectroscopies. High charge carrier mobility is an important parameter for a semiconductive material and depends on the degree of intramolecular order of the discotic molecules in thin films for HBC derivatives. Dipole – dipole interaction and hydrogen bonds were respectively introduced in order to achieve highly ordered supramolecular structure. The self-assembly behavior of these materials were investigated both in solution and solid state. Depending upon the different functionalities, these novel materials show either gelating or non-linear optical properties, which consequently broaden their applications as functional materials. In the field of conceivable electronic devices at a molecular level, HBCs hold high promise. Differently functionalized HBCs have been used as active component in the studies of single-molecular CFET and metal-SAMs-metal junctions. The outstanding properties shown in these materials promise their exciting potential applications in molecular devices.

The Design and Synthesis of Versatile Molecular Building Blocks: Working Towards the Controlled Self-Assembly of Novel Functional Materials

Our research goals are focused on the preparation of novel molecule-based materials that possess specifically designed properties in solution or in the solid state e.g. self-assembly, magnetism, conductivity and spin crossover phenomena. Most of our systems incorporate paramagnetic transition metal ions and the search for new molecule-based magnetic materials is a prominent theme. Specific areas of research include the preparation and study of oxalate based 2D and 3D magnets, probing the versatility of octacyanometalate building blocks as precursors for new molecular magnets, and the preparation of new tetrathiafulvalene (TIF) derivatives for applications in molecular and supramolecular chemistry.

Characterization of the environmental performance of the insulating materials in the enveloping of the building.

Insulating materials in buildings are one of the main factors that should be taken into account when talking about sustainability since with a correct application it could imply important savings for the citizens. In the course of its life, a building requires a series of supplies to perform the duties it has been built for, generating an impact on the environment. The selection of one material or another will establish partly the global environmental impact of the building. Choosing the right insulating material will determine the building's general degree of sustainability, both in its heating savings (energy consumption) and in the environmental impacts caused by its LCA (greenhouse gas emissions). Therefore, we propose to establish guidelines to characterize the insulating material with a better environmental performance in all the stages of its life cycle, taking into account the construction system, the use of the building and its location.

Supramolecular coordination complexes as building blocks for porous and magnetic materials

In this work, new coordination polymers based on two different classes of synthons are presented. In addition, manganese-based metallacrowns of magnetic interest are studied, both in the solid state and in solution. Firstly, functionalized bispyrazolylmethane derivatives are employed as bridging ligands for the establishment of silver-based coordination polymers; the influence of the substituent groups and of the counterions on the supramolecular packing is also investigated. Secondly, the use of metallacrown (MC) complexes as building blocks for porous coordination polymers is discussed. The design of a new metallacrown species is presented, which shows the tendency of aggregating in the solid state to form coordination polymers. Two new coordination polymers are indeed reported, of which one is the first MC-based permanently porous coordination network ever presented. The solid resists solvent evacuation and exhibits gas uptake ability. Furthermore, the isolation and characterization of a new metallacryptate species based on manganese ions is described. The metal-rich structure comprises nine Mn(II)/Mn(III) ions and presents an inverse metallacrown core subunit that binds a μ3-O2- ion. The metallacryptate is isolated in high yields and stable in solution. Lastly, a family of 3d-4f heterometallic metallacrowns is characterized in solution by means of UV-Vis spectrophotometry and of paramagnetically shifted 1H-NMR. The lanthanide-induced shifts observed in the spectra are employed to describe the molecules behaviour in solution and are qualitatively related to the magnetic properties of the compounds.

Managing asbestos in place : a building owner's guide to operations and maintenance programs for asbestos-containing materials.

"July 1990"--Cover.

Building a library collection on blindness and physical disabilities : basic materials and resources.

Mode of access: Internet.

Building a library collection on blindness and physical handicaps : basic materials and resources.

Mode of access: Internet.

The English parish church : an account of the chief building types & of their materials during nine centuries /

Mode of access: Internet.

Building a library collection on blindness and physical handicaps : basic materials and resource.

Mode of access: Internet.

The American builder's general price book and estimator, now first published to elucidate the principles of ascertaining the correct value of every description of artificers' work required in building, from the prime cost of materials and labour in any part of the United States ... to which are added, a variety of useful tables, memorandums, etc.

Microfilm. Ann Arbor, Mich., University Microfilms [n.d.] (American culture series, Reel 35.10)

The builder's pocket manual; containing the elements of building, surveying and architecture. With practical rules and instructions in carpentry, bricklaying, masonry, &c. Observations on the properties of materials and a variety of useful tables and receipts.

Mode of access: Internet.

History and description of the steam-ship Great Britain, built at Bristol for the Great Western Steam-Ship Company: to which are added, remarks on the comparative merits of iron and wood as materials for ship-building.

Includes section of blank pages at end.

Development of sustainable, innovative and energy-efficient concrete, based on the integration of all-waste materials: SUS-CON panels for building applications

The building sector requires the worldwide production of 4 billion tonnes of cement annually, consuming more than 40% of global energy and accounting for about 8% of the total CO2 emissions. The SUS-CON project aimed at integrating waste materials in the production cycle of concrete, for both ready-mixed and pre-cast applications, resulting in an innovative light-weight, ecocompatible and cost-effective construction material, made by all-waste materials and characterized by enhanced thermal insulation performance and low embodied energy and CO2. Alkali activated “cementless” binders, which have recently emerged as eco-friendly construction materials, were used in conjunction with lightweight recycled aggregates to produce sustainable concrete for a range of applications. This paper presents some results from the development of a concrete made with a geopolymeric binder (alkali activated fly ash) and aggregate from recycled mixed plastic. Mix optimisation was achieved through an extensive investigation on production parameters for binder and aggregate. The mix recipe was developed for achieving the required fresh and hardened properties. The optimised mix gave compressive strength of about 7 MPa, flexural strength of about 1.3 MPa and a thermal conductivity of 0.34 W/mK. Fresh and hardened properties were deemed suitable for the industrial production of precast products. Precast panels were designed and produced for the construction of demonstration buildings. Mock-ups of about 2.5 x 2.5 x 2.5 m were built at a demo park in Spain both with SUS-CON and Portland cement concrete, monitoring internal and external temperatures. Field results indicate that the SUS-CON mock-ups have better insulation. During the warmest period of the day, the measured temperature in the SUS-CON mock-ups was lower.

Synthesis and characterization of electron deficient heterocycles as building blocks for electronic materials

This thesis describes the synthesis of a new electropolymerizable viologen derivative. A reasonably high-yielding route is reported, and a preliminary investigation of its polymerisation is described. The viologen and its precursors were examined by 1H NMR, MS, IR and elemental analysis. The energies of the band gap for the materials have been calculated using UV-vis spectroscopy, and cyclic voltammetry was also used to estimate the oxidation and the reduction potentials and to calculate the HOMO and LUMO energies. Theoretical calculations were performed using DFT. The attempted synthesis of a new flavin-functionalised phenanthroline derivative is described. Unfortunately, the protocol used failed to provide the desired compounds.