A novel heteroditopic terpyridine-pincer ligand as building block for mono- and heterometallic Pd(II) and Ru(II) complexes

A palladium-catalyzed Stille coupling reaction was employed as a versatile method for the synthesis of a novel terpyridine-pincer (3, TPBr) bridging ligand, 4'-{4-BrC6H2(CH2NMe2)(2)-3,5}-2,2':6',2 ''-terpyridine. Mononuclear species [PdX(TP)] (X = Br, Cl), [Ru(TPBr)(tpy)](PF6)(2), and [Ru(TPBr)(2)](PF6)(2), synthesized by selective metalation of the NCNBr-pincer moiety or complexation of the terpyridine of the bifunctional ligand TPBr, were used as building blocks for the preparation of heterodi- and trimetallic complexes [Ru(TPPdCl)(tpy)](PF6)(2) (7) and [Ru(TPPdCl)(2)]-(PF6)(2) (8). The molecular structures in the solid state of [PdBr(TP)] (4a) and [Ru(TPBr)(2)](PF6)(2) (6) have been determined by single-crystal X-ray analysis. Electrochemical behavior and photophysical properties of the mono-and heterometallic complexes are described. All the above di- and trimetallic Ru complexes exhibit absorption bands attributable to (MLCT)-M-1 (Ru -> tpy) transitions. For the heteroleptic complexes, the transitions involving the unsubstituted tpy ligand are at a lower energy than the tpy moiety of the TPBr ligand. The absorption bands observed in the electronic spectra for TPBr and [PdCl(TP)] have been assigned with the aid of TD-DFT calculations. All complexes display weak emission both at room temperature and in a butyronitrile glass at 77 K. The considerable red shift of the emission maxima relative to the signal of the reference compound [Ru(tpy)(2)](2+) indicates stabilization of the luminescent (MLCT)-M-3 state. For the mono- and heterometallic complexes, electrochemical and spectroscopic studies (electronic absorption and emission spectra and luminescence lifetimes recorded at room temperature and 77 K in nitrile solvents), together with the information gained from IR spectroelectrochemical studies of the dimetallic complex [Ru(TPPdSCN)(tpy)](PF6)(2), are indicative of charge redistribution through the bridging ligand TPBr. The results are in line with a weak coupling between the {Ru(tpy)(2)} chromophoric unit and the (non)metalated NCN-pincer moiety.

Towards a holistic modelling framework for embodied carbon and waste in the building lifecycle

As the building industry proceeds in the direction of low impact buildings, research attention is being drawn towards the reduction of carbon dioxide emission and waste. Starting from design and construction to operation and demolition, various building materials are used throughout the whole building lifecycle involving significant energy consumption and waste generation. Building Information Modelling (BIM) is emerging as a tool that can support holistic design-decision making for reducing embodied carbon and waste production in the building lifecycle. This study aims to establish a framework for assessing embodied carbon and waste underpinned by BIM technology. On the basis of current research review, the framework is considered to include functional modules for embodied carbon computation. There are a module for waste estimation, a knowledge-base of construction and demolition methods, a repository of building components information, and an inventory of construction materials’ energy and carbon. Through both static 3D model visualisation and dynamic modelling supported by the framework, embodied energy (carbon), waste and associated costs can be analysed in the boundary of cradle-to-gate, construction, operation, and demolition. The proposed holistic modelling framework provides a possibility to analyse embodied carbon and waste from different building lifecycle perspectives including associated costs. It brings together existing segmented embodied carbon and waste estimation into a unified model, so that interactions between various parameters through the different building lifecycle phases can be better understood. Thus, it can improve design-decision support for optimal low impact building development. The applicability of this framework is anticipated being developed and tested on industrial projects in the near future.

Model-based life cycle cost and assessment tool for sustainable building design decision

There is a growing concern in reducing greenhouse gas emissions all over the world. The U.K. has set 34% target reduction of emission before 2020 and 80% before 2050 compared to 1990 recently in Post Copenhagen Report on Climate Change. In practise, Life Cycle Cost (LCC) and Life Cycle Assessment (LCA) tools have been introduced to construction industry in order to achieve this such as. However, there is clear a disconnection between costs and environmental impacts over the life cycle of a built asset when using these two tools. Besides, the changes in Information and Communication Technologies (ICTs) lead to a change in the way information is represented, in particular, information is being fed more easily and distributed more quickly to different stakeholders by the use of tool such as the Building Information Modelling (BIM), with little consideration on incorporating LCC and LCA and their maximised usage within the BIM environment. The aim of this paper is to propose the development of a model-based LCC and LCA tool in order to provide sustainable building design decisions for clients, architects and quantity surveyors, by then an optimal investment decision can be made by studying the trade-off between costs and environmental impacts. An application framework is also proposed finally as the future work that shows how the proposed model can be incorporated into the BIM environment in practise.

Integration of chaos theory and mathematical models in building simulation: Part I: Literature review

Current mathematical models in building research have been limited in most studies to linear dynamics systems. A literature review of past studies investigating chaos theory approaches in building simulation models suggests that as a basis chaos model is valid and can handle the increasingly complexity of building systems that have dynamic interactions among all the distributed and hierarchical systems on the one hand, and the environment and occupants on the other. The review also identifies the paucity of literature and the need for a suitable methodology of linking chaos theory to mathematical models in building design and management studies. This study is broadly divided into two parts and presented in two companion papers. Part (I) reviews the current state of the chaos theory models as a starting point for establishing theories that can be effectively applied to building simulation models. Part (II) develops conceptual frameworks that approach current model methodologies from the theoretical perspective provided by chaos theory, with a focus on the key concepts and their potential to help to better understand the nonlinear dynamic nature of built environment systems. Case studies are also presented which demonstrate the potential usefulness of chaos theory driven models in a wide variety of leading areas of building research. This study distills the fundamental properties and the most relevant characteristics of chaos theory essential to building simulation scientists, initiates a dialogue and builds bridges between scientists and engineers, and stimulates future research about a wide range of issues on building environmental systems.

Integration of chaos theory and mathematical models in building simulation: Part II: Conceptual frameworks

Current mathematical models in building research have been limited in most studies to linear dynamics systems. A literature review of past studies investigating chaos theory approaches in building simulation models suggests that as a basis chaos model is valid and can handle the increasing complexity of building systems that have dynamic interactions among all the distributed and hierarchical systems on the one hand, and the environment and occupants on the other. The review also identifies the paucity of literature and the need for a suitable methodology of linking chaos theory to mathematical models in building design and management studies. This study is broadly divided into two parts and presented in two companion papers. Part (I), published in the previous issue, reviews the current state of the chaos theory models as a starting point for establishing theories that can be effectively applied to building simulation models. Part (II) develop conceptual frameworks that approach current model methodologies from the theoretical perspective provided by chaos theory, with a focus on the key concepts and their potential to help to better understand the nonlinear dynamic nature of built environment systems. Case studies are also presented which demonstrate the potential usefulness of chaos theory driven models in a wide variety of leading areas of building research. This study distills the fundamental properties and the most relevant characteristics of chaos theory essential to (1) building simulation scientists and designers (2) initiating a dialogue between scientists and engineers, and (3) stimulating future research on a wide range of issues involved in designing and managing building environmental systems.

Construction of supramolecular helices and breaking the helicity by forming supramolecular β-sheet structures using suitable self-assembling pseudopeptide building blocks

Bis-valine derivatives or malonamide (Guha,S.; Drew, M.G.B. Small 2008, 4, 1993-2005) and a bis-valine derivative of 1,1-cyclopropone dicarboxamide were used as building blocks for the construction of supramolecular helical structures. The six-membered intramolecular hydrogen-bonded scaffold is formed, and this acts as a unique supramolecular synthon for the construction of a pseudopeptide-based supramolecular helical structure. However, in absence of this intramolecular hydrogen bond. intermolecular hydrogen bonds are formed among the peptide strands. This leads to a supramolecular beta-sheet structure. Proper selection of the supramolecular synthon (six-membered intramolecular hydrogenbonded scaffold) promotes supramolecular helix formation, and a deviation from this molecular structure dictates the disruption of supramolecular helicity. In this study, six crystal structures have been used to demonstrate that a change in the central angle and/or the central core structure of dicarboxamides can be used to design either a supramolecular helix or a beta-sheet.

From CAD to virtual reality: modelling approaches, data exchange and interactive 3D building design tools

Virtual reality has the potential to improve visualisation of building design and construction, but its implementation in the industry has yet to reach maturity. Present day translation of building data to virtual reality is often unidirectional and unsatisfactory. Three different approaches to the creation of models are identified and described in this paper. Consideration is given to the potential of both advances in computer-aided design and the emerging standards for data exchange to facilitate an integrated use of virtual reality. Commonalities and differences between computer-aided design and virtual reality packages are reviewed, and trials of current system, are described. The trials have been conducted to explore the technical issues related to the integrated use of CAD and virtual environments within the house building sector of the construction industry and to investigate the practical use of the new technology.