Over the past few decades, supramolecular self-assembly has become an alternative synthetic tool for constructing targeted discrete molecular architectures. Among various interactions, metal-ligand coordination has attracted great attention owing to high bond enthalpy (15−50 Kcal/mol) and predictable directionality. The basic principle of metal-ligand directed self-assembly relies on the proper designing of information encoded rigid complementary building units (a transition metal based acceptor and a multidentate organic donor) that self-recognize themselves in a chemically reasonable way (depends on their bite angle and symmetry) during self-assembly process. As far as acceptor units are concerned, Pd(II) and Pt(II) metal-based cis-blocked 90° acceptors have so far been used greatly for the construction of a library of 2D/3D discrete supramolecular architectures due to their rigid square planar geometry and kinetic lability. However, in some cases the efforts to design finite supramolecular architectures using a cis-blocked 90° acceptor in combination with a bulky donor ligand were unsuccessful, which may be due to the steric demands of donor ligand. Moreover, the resulted assemblies from such cis-blocked 90° building unit are mostly non-fluorescent in nature and limit the possibility of using them as chemosensors for various practical applications. Unlike that of rigid square-planar Pt(II) and Pd(II)-metal based building blocks, the use of other transition metal-based building units for the construction of discrete nanoscopic molecular architectures are known to lesser extent, mainly because of their versatile coordination geometries. However, some of the half-sandwiched piano-stool complexes of late transition metals like Ru, Os, Ir and Rh are known to maintain the stable octahedral geometry under various reaction conditions. Moreover, the self-assembly using redox active transition metal-based building units may lead to redox active assemblies. On the other hand, symmetrical rigid donors have been widely used as the favorite choices for the purpose of constructing desired product mainly due to their predictable directionality. Flexible linkers are not predictable in their directionality during self-assembly process and thus results mostly in undesired polymeric products. Furthermore, metal-ligand directed self-assembly provides opportunity to introduce multifunctionality in a single step within/onto the final supramolecular architectures. Among various functional groups, the incorporation of unsaturated ethynyl functionality is expected to enrich the final assemblies to be π-electron-rich and the attachment of ethynyl functionality with heavy transition metal ions are known to be luminescent in nature due to the facile metal to ligand charge transfer (MLCT). Hence, the final supramolecular complexes can be used as potential fluorescence sensors for electron-deficient nitroaromatics, which are the chemical signature of most of the commercially available explosives. The main thrust of the present investigation is focused on the judicious design and syntheses of multifaceted 2D/3D supramolecular architectures of finite shapes, sizes and functionality using Pt(II)/Ru(II) based “shape-selective” organometallic building blocks and investigation of their application as chemosensors. CHAPTER 1 of the thesis presents a general review on the core concepts of self-assembly and supramolecular chemistry. In particular, it underlines the importance of metal-ligand directional bonding approach for designing a vast plethora of discrete 2D/3D supramolecular architectures with tremendous variation in topology. CHAPTER 2 describes the design and syntheses of a series of 2D metallamacrocycles using carbazole-functionalized shape-selective 90° building units. A new Pt2II organometallic 90° acceptor 3,6-bis[trans-Pt(PEt3)2(NO3)(ethynyl)]carbazole (M1) containing ethynyl functionality is synthesized via Sonagashira coupling reaction and characterized. The combination of M1 with three different flexible ditopic donors (L1−L3) afforded [2 + 2] self-assembled molecular squares (1−3), respectively [where L1 = 1,3-bis(4-pyridyl)isophthalamide; L2 = 1,3-bis(3-pyridyl)isophthalamide; L3 = 1,2-bis(4-pyridyl)ethane] (Scheme 1). Scheme 1: Schematic presentation of the formation of a series of [2 + 2] self-assembled molecular squares. An equimolar (1:1) combination of same acceptor M1 with rigid linear ditopic donors (L4-L5) yielded [4 + 4] self-assembled octanuclear molecular squares 4 and 5, respectively [L4 = 4,4’-bipyridine; L5 = trans-1,2-bis(4-pyridyl)ethylene]. Conversely, a similar reaction of M1 with an amide-based unsymmetrical linear flexible ditopic donor L6 resulted in the formation a [2 + 2] self-sorted molecular rhomboid (6a) as a single product [L6 = N-(4-pyridyl)isonicotinamide]. Despite the possibility of several linkage isomeric macrocycles (rhomboids, triangles and squares) due to different connectivity of the ambidentate linker, the formation of a single and symmetrical molecular rhomboid 6a as an exclusive product is an interesting observation. This chapter also presents the synthesis and characterization of a complementary 90° dipyridyl donor 3,6-bis(4-pyridylethynyl)carbazole (L7). Stoichiometric combination of L7 with several PdII/PtII-based 90° acceptors (M2−M4) yielded [2 + 2] self-assembled molecular “bowl” shaped macrocycles (7−9) respectively, in good yields [M2 = cis-(dppf)Pd(CF3SO3)2; M3 = cis-(dppf)Pt(CF3SO3)2; M4 = cis-(tmen)Pd(NO3)2]. All these newly synthesized macrocycles were characterized by various spectroscopic techniques and molecular structures of some of them were confirmed by single crystal X-ray diffraction analysis. In addition to their syntheses and characterization, fluorescence chemosensing ability for various analytes was investigated. Macrocycle 1 is a system composed of amide-based receptor units and carbazole-based fluorophore moieties. The fluorescence study of 1 elicited a dramatic enhancement in the fluorescence intensity upon gradual addition of P2O74- anion in DMF/H2O solvent mixture, whereas similar titration under identical condition with other anions like F-, ClO4-, and H2PO4- did not show such change. Hence, molecular square 1 can be used as selective fluorescence sensor for pyrophosphate (P2O74-) anion. Due to their extended π-conjugation, macrocycles 3-4 were used as fluorescence sensors for electron-deficient nitroaromatics, which are the chemical signatures of many commercially available explosives. The fluorescence study showed a marked quenching of initial fluorescence intensity of the macrocycles(3-4) upon gradual addition of picric acid (PA) and they exhibited large fluorescence quenching responses with high selectivity for nitroaromatics among various other electron deficient aromatic compounds tested. As macrocycle 7 has large concave aromatic surface, it was utilized as a suitable host for large convex guest such as fullerene C60. The fluorescence quenching titration study suggested that macrocycle 7 forms a stable ~1:1 host-guest complex with C60 and the calculated association constant (KSV) is 1.0 × 105 M-1. CHAPTER 3 presents two-component coordination-driven self-assembly of a series of [2 + 2] molecular rectangles and a [2 + 4] self-assembled molecular tetragonal prism. An equimolar combination of pre-designed linear PtII2-acceptors M5−M6 separately with three different “clip” donors (L2, L8−L9) led to the formation of [2 + 2] self-assembled tetranuclear cationic molecular rectangles (10−15), respectively [M5 = 1,4-bis[trans-Pt(PEt3)2(NO3)(ethynyl)] benzene; M6 = 4,4’-bis[trans-Pt(PEt3)2(CF3SO3)(ethynyl)]biphenyl; L8 = 1,3-bis(3-pyridyl)ethynylbenzene; L9 = 1,8-bis(4-pyridyl)ethynylanthracene]. Rectangles 10-15 showed strong fluorescence in solution owing to their extended π-conjugation. Amide-functionalized rectangle 10 was used as a macrocyclic receptor for dicarboxylic acids. Solution state fluorescence study showed that rectangle 10 selectively binds (KSV = 1.4 × 104 M-1) with maleic acid by subsequent enhancement in emission intensity and addition of other analogous aliphatic dicarboxylic acids such as fumaric, succinic, adipic, mesaconic and itaconic acids causes no change in the emission spectra; thereby demonstrated its potential use as macrocyclic receptor in sensor applications. Since rectangle 15 is enriched with π-conjugation, it was examined as a fluorescence sensor for electron-deficient nitroaromatics such as picric acid, which is often considered as a secondary chemical explosive. The fluorescence study of 15 showed a significant quenching of initial emission intensity upon titrating with picric acid (PA) and it exhibited the largest fluorescence quenching response with high selectivity for picric acid. Scheme 2: Schematic representation of formation of [2 + 4] self-assembled of molecular tetragonal prism. This chapter also describes two-component coordination [2 + 4] self-assembly of a pyrene-based PtII8 tetragonal prism (16) as shown in Scheme 2, using a newly designed tetratopic organometallic acceptor (M7; 1,3,6,8-tetrakis[trans-Pt(PEt3)2(NO3)(ethynyl)]pyrene) in combination with an amide-based “clip” donor (L2) and propensity of this prism (16) as a selective fluorescence sensor for nitroaromatic explosives has been examined both in solution as well as in thin-film. CHAPTER 4 reports the synthesis and structural characterization of a series of Ru(II)-based bi-and tetra-nuclear metallamacrocycles and hexanuclear trigonal prismatic cages. In principle, the self-assembly of a “clip” acceptor with an asymmetrical ditopic donor is expected to give two different linkage isomeric (head-to-tail and head-to-head) molecular rectangles because of different bond connectivity of the donor. However, the equimolar combination of half-sandwiched p-cymene binuclear Ru(II)-based “clip” acceptors (M8−M9) and an amide-based ambidentate donor (L6) resulted in the self-sorting of single linkage (head-to-tail) isomeric rectangles 17−18 as only products, respectively [M8 = [Ru2(μ-η4-C2O4)(MeOH)2(η 6-p-cymene)2](CF3SO3)2; M9 = [Ru2(μ- η4-C6H2O4)(MeOH)2(η 6-p-cymene)2](CF3SO3)2]. Molecular structures of these head-to-tail linkage isomeric rectangles were unambiguously proved by single crystal X-ray diffraction analysis. Likewise, the self-assembly of oxalato-bridged Ru(II) acceptor M8 with a rigid dipyridyl “clip” donor L8 yielded a tetranuclear cationic pincer complex 19, while a similar reaction of M8 with an anthracene-functionalized “clip” donor L9 having shorter distance (between their reactive sites) compared to L8 led to the formation of [1 + 1] self-assembled macrocycle 20. This chapter also represents the design and synthesis of two hexanuclear trigonal prismatic cages (21−22) from the self-assembly of a π-electron rich tripyridyl donor (L10; 1,3,5-tris(4-pyridylethynyl)benzene) in combination with binuclear acceptors M8 and M9, respectively (Scheme 3). Formation of these prismatic cages was initially characterized using various spectroscopic techniques and the molecular structure of oxalato-bridged prism 21 was confirmed by single crystal X-ray diffraction analysis. In addition to the structural characterization, the pincer complex 19 and trigonal prismatic cages 21−22 were used as fluorescence sensors for nitroaromatic explosives owing to their large internal porosity and their π-electron rich nature. Scheme 3: Schematic representation of the formation of [3 + 2] self-assembled trigonal prismatic cage. CHAPTER 5 covers the syntheses of a few discrete metallamacrocycles using flexible imidazole/carboxylate based donors instead of much widely employed polypyridyl donors. The metal-ligand directed self-assembly of oxalato-bridged acceptor M8 and an imidazole-based tetratopic donor (L11; 1,2,4,5-tetrakis(imidazol-1-yl)benzene) in methanol afforded [2 + 1] self-assembled tetranuclear macrocycle 23. Conversely, the similar combination of L11 with 2,5-dihydroxy-1,4-benzoquinonato-bridged binuclear complex (M9) in 1:2 molar ratio in methanol resulted in an octanuclear cage 24. Both the complexes (23−24) were isolated as their triflate salts in high yields and were characterized by various spectroscopic methods including single crystal X-ray diffraction analysis. Scheme 4: Schematic representation of formation of an octanuclear incomplete Ru(II) open prism via ruthenium-oxygen coordination driven self-assembly. This chapter also explains the self-sorting of an unusual octanuclear incomplete prism [Ru8(η6-p-cymene)8(tma)2(μ-η4-C2O4)2(OMe)4](CF3SO3)2 (25) via ruthenium-oxygen coordination driven self-assembly of building block M8 and sodium benzene-1,3,5-tricarboxylate (L12) (Scheme 4). Electronic absorption study indicated that prism 25 exhibited a remarkable shape-selective binding affinity for 1,3,5-trihydroxybenzene (phluoroglucinol) via multiple hydrogen bonding interactions and such shape-selective binding was confirmed by single crystal X-ray diffraction analysis. (For figures pl see the abstract file)

The theme of this thesis is continue on examining relatively commonly used measurement flow field metods, which assessing the variables flows at a high level. Thesis follow up mainly the flow field in the channel bottom boundary-layer and its depending on different factors. To calculate velocity in boundary-layer is common used extrapolation method, because this boundary layer is only the small part of measuring cross section. Increase the accuracy of measurement of flow variables make the flow in the boundary layer also important. Thesis is a summary of a basic theory of flow field, but mainly is about dependent local flow velocity on position, and about deformation of flow field in boundary layer. The aim thesis is description different calculation methods of flow flow field in boundary layer and comparison to with real condition which was measured in laboratory UVS-LVV. Real condition flow field in channel bottom boundary layer is based on exact method Particle image velocimetry. The measurement results serve to compare commonly used calculation methods or different theories velocity in the channel bottom boundary layer. Outputs this thesis offers comparison, confirmation or specification calculation methods according to the results. It has been suggested several limitations on certain methods of calculation, or coefficient were modified or alternative has been proposed to calculate them.

Batteries are promising sources of green and sustainable energy that have been widely used in various applications. Lithium-ion batteries (LIBs) have an important role in the energy storage sector due to its high specific energy and energy density relative to other rechargeable batteries. The main challenges for keeping the LIBs to work under safe conditions, and at high performance are strongly related to the battery thermal management. In this study, a critical literature review is first carried out to present the technology development status of the battery thermal management system (BTMS) based on air and liquid cooling for the application of battery energy storage systems (BESS). It was found that more attention has paid to the BTMS for electrical vehicle (EV) applications than for stationary BESS. Even though the active forced air cooling is the most commonly used method for stationary BESS, limited technical information is available. Liquid cooling has widely been used in EV applications with different system configurations and cooling patterns; nevertheless, the application for BESS is hard to find in literature.To ensure and analyze the performance of air and liquid cooling system, a battery and thermal model developed to be used for modeling of BTMS. The models are based on the car company BMW EV battery pack, which using Nickel Manganese Cobalt Oxide (NMC) prismatic lithium-ion cell. Both air and liquid cooling have been studied to evaluate the thermal performance of LIBs under the two cooling systems.According to the result, the air and liquid cooling are capable of maintaining BESS under safe operation conditions, but with considering some limits. The air-cooling is more suitable for low surrounding temperature or at low charging/discharge rate (C-rate), while liquid cooling enables BESS to operate at higher C-rates and higher surrounding temperatures. However, the requirement on the maximum temperature difference within a cell will limits the application of liquid cooling in some discharge cases at high C-rate. Finally, this work suggests that specific attention should be paid to the pack design. The design of the BMW pack is compact, which makes the air-cooling performance less efficient because of the air circulation inside the pack is low and liquid cooling is more suitable for this type of compact battery pack.

This investigation identifies how CAD models of typical automotive body assemblies could be defined to allow a continuous optimisation of the number of iterations required for the final design and the number of variants on the basis of Parametric Associative Design (PAD) and how methodologies for the development of surfaces, parts and assemblies of the automotive body can be represented and structured for a multiple re-use in a collaborative environment of concept phase of a Product Evolution (Formation) Process (PEP). The standardisation of optimised processes and methodologies and the enhanced interaction between all parties involved in product development could lead to improve product quality and reduce development time and hence expenses. The fundamental principles of PAD, the particular methodologies used in automotive body design and the principles of methodical development and design in general are investigated. The role which automotive body engineers play throughout the activities of the PEP is also investigated. The distribution of design work in concept teams of automotive body development and important methodologies for the design of prismatic profile areas is critically analysed. To address the role and distribution of work, 25 group work projects were carried out in cooperation with the automotive industry. Large assemblies of the automotive bodies were developed. The requirements for distributed design work have been identified and improved. The results of the investigation point towards a file based, well structured administration of a concept design, with a zone based approach. The investigation was extended to the process chain of sections, which are used for development of surfaces, parts and assemblies. Important methods were developed, optimised and validated with regard to an update safe re-use of 3D zone based CAD models instead of 2D sections. The thesis presents a thorough description of the research undertaken, details the experimental results and provides a comprehensive analysis of them. Finally it proposes a unique methodology to a zone based approach with a clearly defined process chain of sections for an update-safe re-use of design models.

Designing mechanical products in a competitive environment can present unique challenges, and designers constantly search for innovative ways to increase efficiency. One way to save space and reduce cost is to use ortho-planar compliant mechanisms which can be made from sheets of material, or lamina emergent mechanisms (LEMs). This thesis presents principles which can be used for designing LEMs. Pop-up paper mechanisms use topologies similar to LEMs, so it is advantageous to study their kinematics. This thesis outlines the use of planar and spherical kinematics to model commonly used pop-up paper mechanisms. A survey of common joint types is given, as well as an overview of common monolithic and layered mechanisms. In addition, it is shown that more complex mechanisms may be created by combining simple mechanisms in various ways. The principles presented are applied to the creation of new pop-up joints and mechanisms, which also may be used for lamina emergent mechanisms. Models of the paper mechanisms presented in Chapter 2 of the thesis are found in the appendix, and the reader is encouraged to print, cut out and assemble them. One challenge associated with spherical and spatial LEM design is creating joints with the desired motion characteristics, especially where complex spatial mechanism topologies are required. Hence, in addition to a study of paper mechanisms, some important considerations for designing joints for LEMs are presented. A technique commonly used in robotics, using serial chains of revolute and prismatic joints to approximate the motion of complex joints, is presented for use in LEMs. Important considerations such as linkage configuration and mechanism prototyping are also discussed. Another challenge in designing LEMs is creating multi-stable mechanisms with the ability to have coplanar links. A method is presented for offsetting the joint axes of a spatial compliant mechanism to introduce multi-stability. A new bistable spatial compliant linkage that uses that technique is introduced. In the interest of facilitating LEM design, the final chapter of this thesis presents a preliminary design method. While similar to traditional methods, this method includes considerations for translating the mechanism topology into a suitable configuration for use with planar layers of material.