本論文對炔銀化合物提出系統性的合成和結構硏究，使用一種新型的多核屬的超分子合成子，從而建構出一系配位元網絡。 / 我們開發出同的結晶技術，在PhC≡C⊃Agn (n = 3, 4, 5)超分子合成子，通過加入同銀鹽，從而相對地獲得獲得銀鏈4AgC≡CPh・10AgCF₃CO₂・8DMSO (4)，層銀銀平面AgC≡CPh・AgNO₃ (1) 和2AgC≡CPh・AgNO₃ (2)，粗銀柱5AgC≡CPh・AgNO₃AgCF₃SO₃・2DMSO (5)，陽子銀柱[Ag₅(PhC≡C)₄(DMSO)₂]X (X = ClO₄, BF₄, PF₆, AsF₆ and SbF₆) (3)。 / 上述結果鼓我們展開進一步的硏究，通過改變芳香環上取代基的性質或位置 (F, Cl, Br, I, Me, C(=O)CH₃, NO₂ 和 C≡N) 產出同的銀結構，如鏈，柱，帶，層，三維多孔配位聚合物，以及多面體銀柱。如，化合物[(NO₃)@Ag₁₅(C≡CC₆H₄F-2)₁₀](NO₃)₄ (15)內有一個硝酸子作為模板所組成的十五核橄欖形銀簇多面體。此 Ag₁₅簇可接在一起，形成一條銀鏈。個硝酸子被包裏在一個 Ag₂₆花生雙中，花生銀雙繫在一起並形成一條多面體銀柱[(NO₃)₂@Ag₂₆(C≡CC₅H₄Me-2)₁₆](NO₃)₈ (23)。 / 在炔銀超分子合成子中，銀烯基和銀氰基相互作用發揮重要作用生成二維有機銀網絡AgC≡CCH₂OC₆H₄(CH=CH₂-2) · 6AgCF₃CO₂ · 3H₂O (31) 和2AgC≡CC₆H₄(C≡N-4) · 4AgO₂CCF3 · 2DMSO · H₂O (36)。 / 多環芳烴(PAHs)中的 π 電子體系具有鍵合屬子的能。此陽子與 π 電子間的相互作用提供一個潛在有效的做法去建新型固態結構。我們的構思是硏究 π-π 堆積和銀雜環作用，在RC≡C⊃Agn (n = 4, 5; R = 萘基或喹啉基) 超分子合成子建設配位聚合物。在(C₁₀H₇C≡C-1)Ag · 3AgO₂CCF₃ · 3H₂O (38) 和 (C₁₀H₇C≡C-2)Ag · 3AgO₂CCF₃ · 2H₂O · MeCN (39) 中，Ag-π 作用成功引進在炔銀超分子合成子系統。分子間的 π-π 堆積作用有助於炔銀化合物的超分子合成子組裝 Ag(1-NC₉H₆C≡C-2) · 3AgO₂CCF₃ · 3H₂O (44) 和 Ag(1-NC₉H₆C≡C-4) · 3AgO₂CCF₃ · 2H₂O (47)。 / 傳統上，陰子模板是合成高核密堆積銀簇合物的簡方法。銀簇合物的核密堆積可以通過調整陰子模板的大小和使用同炔基配體。在使用巨型多酸(POMs)陰子，Mo₆O₂₂⁸⁻，形成一個龐大的十核炔銀簇合物後，我們硏究出另一種方法合成高核密堆積銀簇合物。一個形十二面體十四核炔銀簇合物通過在溶液中的重新組裝過程產生出三十八核炔銀簇合物，把在小銀簇合物中的氯模板轉化為偽八面體Cl₆Ag₈核心的巨型簇合物 Ag₃₈C₁[₆(tBuC≡C)₂₀(ClO₄)₁₂ · Et₂O (48) 和Ag₃₈C₁₆(chxC≡C)₂₀(ClO₄)₁₂ · 1.5Et₂O (49). / This thesis presents a systematic synthetic and structural study of silver(I) ethynide complexes employing a new kind of polynuclear metal-ligand supramolecular synthon for the construction of silver(I) coordination networks. / We have developed different crystallization techniques in the supramolecular assembly of the Ph-C≡C⊃Ag[subscript n] (n = 3, 4, 5) metal-ligand synthon and various anions to obtain an infinite silver(I) chain in 4AgC≡CPh10AgCF₃CO₂・8DMSO (4), silver(I) layers in 2AgC≡CPh・AgNO₃(2) and AgC≡CPh・AgNO₃ (1), a thick silver(I) column in 5AgC≡CPh・AgNO₃・AgCF₃SO₃・2DMSO (5), and cationic silver(I) columns in [Ag₅(PhC≡C)₄(DMSO)₂]X (X = ClO₄, BF₄, PF₆, AsF₆ and SbF₆) (3). / The above results encouraged us to carry out further investigation through variation of the nature or position of substituents (F, Cl, Br, I, Me, C(=O)CH₃, NO₂ and C≡N) on the aromatic ring to yield silver(I) chain, column, ribbon, layer, and 3D porous coordination polymers, as well as a polyhedral silver(I) column. For example, an oliveshaped Ag₁₅ core exists in [(NO₃)@Ag₁₅(C≡CC₆H₄F-2)₁₀](NO₃)₄ (15), in which the encapsulated nitrate ion acts as a template for the formation of the Ag₁₅ cluster. Such Ag₁₅ clusters are then joined together to form a polymeric silver(I) chain. Peanut-shaped silver(I) double cages, each formed from two nitrate ions encapsulated within a Ag₂₆ cage, are linked together to form a polyhedral silver(I) chain in [(NO₃)₂@Ag₂₆(C≡CC₅H₄Me-2)₁₆](NO₃)₈ (23). / The silver(I)-ethynide supramolecular synthon participating in silver(I)vinyl and silver(I)cyano interactions plays an important role to generate 2-D silver-organic networks in AgC≡CCH₂OC₆H₄(CH=CH₂-2) · 6AgCF₃CO₂ · 3H₂O (31) and 2AgC≡CC₆H₄(C≡N-4) · 4AgO₂CCF3 · 2DMSO · H₂O (36). / The π-electron system of polycyclic aromatic hydrocarbons (PAHs) is known to be capable of bonding to metal ions. The exploitation of such cation-π interactions provides a potentially fruitful approach to building novel solid-state architectures. Our conceived idea is to investigate the π-π stacking and silver(I)-heteroaromatic interactions for the construction of coordination polymers using the R-C≡C⊃Ag[subscript n] (n = 4, 5; R = naphthalenylethynide or quinolinylethynide) supramolecular synthon. In the compounds (C₁₀H₇C≡C-1)Ag · 3AgO₂CCF₃ · 3H₂O (38) and (C₁₀H₇C≡C-2)Ag · 3AgO₂CCF₃ · 2H₂O · MeCN (39), silver-π interaction has been successfully introduced into silver(I)ethynide systems. Intermolecular π-π interaction contributes to the assembly of supramolecular synthons in compounds Ag(1-NC₉H₆C≡C-2) · 3AgO₂CCF₃ · 3H₂O (44) and Ag(1-NC₉H₆C≡C-4) · 3AgO₂CCF₃ · 2H₂O (47). / Traditionally, anion templates are used in a facile approach for the synthesis of high-nuclearity silver(I) clusters. The cluster nuclearity can be controlled by adjusting the size of the templating anions and by using different alkynyl ligands. After using the giant polyoxometalates (POMs) anion, Mo₆O₂₂⁸⁻, to form a large Ag₆₀ alkynyl cluster, we have developed another approach to synthesize high-nuclearity silver(I) clusters. Generation of a Ag₃₈ ethynide cluster from a rhombic dodecahedral Ag₁₄ ethynide cluster as precursor occurs in solution via a re-assembly process that involves transformation of the encapsulated chloride template in the small cluster into a pseudo-Oh Cl6Ag8 core in the giant cluster complexes Ag₃₈C₁₆([superscript t]BuC≡C)₂₀(ClO₄)₁₂ · Et₂O (48) and Ag₃₈C₁₆(chxC≡C)₂₀(ClO₄)₁₂ · 1.5Et₂O (49). / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Cheng, Ping Shing. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2012. / Includes bibliographical references (leaves 216-225). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese. / Chapter Acknowledgment --- p.i / Chapter Abstract --- p.ii / Chapter Table of Contents --- p.vi / Chapter Index of Compounds --- p.viii / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Coordination Polymers and Supramolecular Architectures --- p.1 / Chapter 1.1.1 --- Influence of Metal Cations --- p.2 / Chapter 1.1.2 --- Influence of Spacer Ligands --- p.3 / Chapter 1.1.3 --- Influence of Counter Anions --- p.4 / Chapter 1.1.4 --- Influence of Crystallization Techniques --- p.6 / Chapter 1.2 --- Argentophilic Interaction --- p.7 / Chapter 1.2.1 --- Multinuclear Silver-Ethynide Aggregates and Discrete Molecules --- p.9 / Chapter 1.2.1.1 --- Silver(I)-Ethynide Aggregates to Multi-dimensional Structures --- p.10 / Chapter 1.2.1.2 --- High-Nuclearity Homo- and Hetero-d¹° Metal Alkynyl Clusters --- p.13 / Chapter 1.2.2 --- Argentophilic chain and column --- p.15 / Chapter 1.2.3 --- Argentophilic layer --- p.18 / Chapter 1.3 --- Supramolecular Synthons in Crystal Engineering --- p.20 / Chapter 1.3.1 --- Coordination Chemistry of silveralkynyl complexes --- p.22 / Chapter 1.3.2 --- Coordination Chemistry of silveralkene complexes --- p.25 / Chapter 1.3.3 --- Coordination Chemistry of silveraromatic complexes --- p.26 / Chapter 1.4 --- Research strategy and Plan --- p.29 / Chapter Chapter 2 --- Argentophilic Infinite Chain, Column and Layer Structures Assembled with the Multinuclear Silver(I)Phenylethynide Supramolecular Synthon Syntheses of Silver(I)- Ethynide Complexes --- p.32 / Discussion --- p.52 / Conclusion --- p.55 / Chapter Chapter 3 --- Assembly of Multinuclear Supramolecular Synthon X-C₆H₄-C≡C⊃Ag[subscript n] (n = 3, 4; X = F, Cl, Br, I) Incorporating Isomeric Halophenylethynides and Silver Nitrate --- p.57 / Discussion --- p.84 / Summary --- p.86 / Chapter Chapter 4 --- Supramolecular Assembly of Silver(I) Alkyl and Aryl Ethynide with Silver(I) Nitrate in the Formation of Argentophilic Layers --- p.87 / Discussion --- p.121 / Summary --- p.122 / Chapter Chapter 5 --- Assembly of Organometallic Networks with Bifunctional Multinuclear Silver(I)-Ethynide Supramolecular Synthons and Silver Trifluoroacetate --- p.123 / Discussion --- p.149 / Summary --- p.151 / Chapter Chapter 6 --- Network Assembly with Multinuclear Silver(I) Naphthalenyl and Quinolinyl Ethynide Supramolecular Synthons R-C≡C⊃Ag[subscript n] (n = 4, 5) --- p.152 / Discussion --- p.179 / Summary --- p.180 / Chapter Chapter 7 --- Enlargement of Globular Silver Ethynide Cluster via Core Transformation and Re-Assembly --- p.181 / Discussion --- p.187 / Conclusion --- p.189 / Chapter Chapter 8 --- Experimental Section --- p.190 / Chapter 8.1 --- General --- p.190 / Chapter 8.2 --- Preparation of polymeric silver(I) ethynide complexes --- p.190 / Chapter 8.3 --- Preparation of complexes 1-49 --- p.196 / Chapter 8.4 --- X-Ray Crystallographic Analysis --- p.215 / References --- p.216 / Chapter Appendix I --- Publication Based on Research Findings --- p.226 / Chapter Appendix II --- Crystal Data --- p.228 / Chapter Appendix III --- Atomic Coordinates, Thermal Parameters, Bonds Lengths and Bond Angle (Available as an Electronic File) --- p.239

Chapter 1 includes the Introduction and literature review which describes current developments within the field of in vitro/vivo imaging of cancers, with a particular emphasis on the techniques employing fluorescence emission-based spectroscopy and imaging modalities. Examples are cited whereby graphene and its congeners have been used in conjunction with various fluorophores and peptide sequences as a means of achieving highly specific imaging probes. This section discusses aspects of energy transfer and the possibility that molecular probes can be designed to achieve both therapeutic goals and diagnosis (Theranostics). This review concludes with a discussion of the use of organic supramolecularly assembled imaging agents as a means of achieving thermodynamically controlled nano-constructs for the functionalisation of graphenes and their potential future applications as theranostic agents. Chapters 2, 3 and 4 describe the synthesis of chiral and naphthalene diimides (NDIs) which are fluorescent. Spectroscopic investigations in the solution phase are described and the propensity for aggregation in these systems is discussed. The specific nature of the self-assembly processes involved is explored in different solvent systems and in the solid state. Fluorescence lifetime imaging microscopy (FLIM) and laser scanning confocal microscopy (LSCM) are used to investigate the cellular uptake of the NDI molecules and their capacity to image living prostate cancer cells (PC-3). The NDIs are subsequently complexed supramolecularly to poly-aromatic carbon systems such as C60 and coronene (Chapter 3), as well as thermally reduced graphene oxide (Chapter 4). Chapter 3 describes the explorations into the modelling of the donor-acceptor interactions between the NDIs and the C60/coronene in order to establish binding stoichiometry and association constants. Both Chapters 3 and 4 discuss fluorescence titration and time correlated single photon counting (TCSPC) experiments which were performed as a means of establishing the presence of excited state energy transfer mechanisms. The chapters conclude with investigations in living cells in order to establish retention of in vitro fluorescence, with particular attention being paid to confirming the graphene complex stability. Chapter 5 describes the synthesis and functionalisation of a seven amino acid sequence peptide known as the G-receptor protein (GRP) binding unit of the polypeptide bombesin. The sequence binds GRPs that are known to be up-regulated in prostate cancer carcinoma and it has been widely utilised in the literature as a means of enhancing the up-take of various cancer imaging agents that employ a variety of imaging modalities. The peptide was attached to the fluorescent NDIs via carbodiimide activation protocols with the purpose of providing added specificity to the imaging agent with respect to PC-3 cells. Prior to NDI derivatisation with bombesin, electrochemical impedance spectroscopy (EIS) has been performed to establish the extent to which the peptide sequence binds to prostate cancer cells over healthy ones. The chapter concludes with confocal microscopy of the bombesin derivative NDI complexed to thermally reduced graphene oxide as a means of validating the utility of the fluorescent targeted bioconjugate as synthetic scaffolds for future early diagnosis and sensing devices for prostate cancer. Chapter 6 constitutes the summary of this work and highlights several possible areas of future developments of relevance to the results discussed and related future experiments proposed to fully validate the device assembly for prostate cancer sensing. Chapter 7 contains the Experimental section and the relevant data gathered over the course of the investigations. Additional supporting figures or data referred to but not included in the main text of the thesis are reported in the Appendices.

Herein we describe a straight-forward and reproducible method for the preparation of homogeneous, multicomponent cocrystals and supramolecular solid solutions. We prepared these multicomponent materials based on small organic molecules that employ a two-point supramolecular hydrogen bond synthon. We report the creation and characterization of two, three, four, five, and seven component crystals containing a variety of 2-aminopyridines and monosubstituted benzoic acids. These systems exhibit the ability to accommodate multiple components in varying proportions while coordinating into an identical packing structure. The flexibility of the system to incorporate multiple components also gives rise to gradual modulation of physical properties.

A construção de sistemas metal-orgânicos supramoleculares através da exploração da conectividade de ligantes terpiridínicos e o desenvolvimento de suas aplicações em nanodispositivos, são tratados nesta tese. Foram desenvolvidos novos complexos de ferro e rutênio com ligantes terpiridínicos funcionalizados, capazes de gerar filmes finos e apresentar interações supramoleculares do tipo hóspede-hospedeiro. Esses complexos foram empregados na modificação de superfícies de dióxido de titânio, visando aplicações em sensores e dispositivos fotoeletroquímicos. Modificando-se o dióxido de titânio nanocristalino, com moléculas hospedeiras de carboxi-metil-β-ciclodextrina, foi possível gerar um sistema seletivo para fotodegradação de compostos aromáticos, como demonstrado para o complexo bis(4\'-(4-bromo-fenil)-2,2\':6\',2\'\'-terpiridina)ferro(II), cujo descoramento foi observado efetuando-se a fotoirradiação no ultravioleta. Esse sistema foi aprimorado para gerar um dosímetro de UV, com base nesse princípio. Além disso, foram feitos estudos de eletropolimerização desse complexo e sobre a capacidade dos filmes moleculares gerados, de atuarem em sensores amperométricos na detecção de espécies químicas relevantes, como os íons nitrito. Outro complexo sintetizado foi o [Ru(c-ph-terpy)(Q)(NCS)], em que c-ph-terpy é a 4\'-(4-carboxi-fenil)-2,2\':6\',2\'\'-terpiridina e Q é o ligante 8-oxiquinolinato. Esse complexo terpiridínico foi desenvolvido para ser utilizado como fotossensibilizador em células solares do tipo Grätzel, tanto na forma direta, como após a modificação da superfície de dióxido de titânio com a carboxi-metil-β-ciclodextrina. Demonstrou-se que através da sua inclusão na cavidade supramolecular, o fotossensibilizador aumenta a eficácia da fotoconversão de energia. Finalmente, foi sintetizada uma nova supermolécula a partir da auto-montagem coordenativa entre a tetra-piridilporfirina e complexos de rutênio(II) coordenados com ligantes oxalato e 4-cloro-2,2\':6\',2\'\'-terpiridina. Foi observado que essa supermolécula apresenta atividade catalítica de oxidação de substratos orgânicos, associada aos grupos periféricos. Os vários sistemas estudados possibilitaram avançar nas estratégias de engenharia supramolecular, através da construção de novos conectores, blocos de montagem e filmes moleculares, bem como avaliar algumas de suas aplicações nanotecnológicas. / This thesis deals with the development of new metal-organic supramolecular systems based on functionalized terpyridine compounds, including their application in nanotechnological devices. New iron and ruthenium coordination compounds incorporating terpyridine ligands have been obtained, and their ability to generate thin films and participate in host-guest interactions has been conveniently explored. Such complexes have been employed in the modification of titanium dioxide surfaces, for applications in sensors and photoeletrochemical cells. By combining nanocrystalline titanium dioxide with carboxy-methyl-β-cyclodextrin, a novel, efficient strategy has been devised for photodegradation of aromatic compounds, and successfully demonstrated after anchoring the bis(4\'-(4-bromophenyl)-2,2\':6\'2\'\'-terpyridine)iron(II) complex and monitoring its bleaching by exposing to UV radiation. In this way, this system has been successfully employed in the design of a novel, versatile UV dosimeter. Electropolymerization studies have also been carried out on this complex, in order to generate molecular films for use in amperometric sensors, capable of probing relevant species, such as the nitrite ions. Another compound dealt with in this work was [Ru(c-ph-terpy)(Q)(NCS)], where c-ph-terpy = 4\'-(4-carboxy-pheny)-2,2\':6\',2\'\'-terpyridine, and Q = 8-oxyquinolinate ligand. This terpyridine complex has been designed as fotosensitizer in Grätzel\'s photoelectrochemical cells, by its direct coating on the titanium dioxide nanoparticles or by performing their previous treatment with carboxi-methyl-β-cyclodextrin. It has been shown that the inclusion into the cyclodextrin cavity improves the performance of the photosensitizer for energy conversion. Finally, a new supermolecule encompassing a central tetrapyridylporphyrin unity attached to four chloro(oxalate)(4-chloro-2,2\':6\',2\'\'-terpyridine)ruthenium(II) complexes, has been synthesized. This species exhibits catalytic activity in the oxidation of organic compounds. The reported study, involving several systems, has contributed to the available molecular engineering strategies, through the building up of new connecting groups and molecular films, and has also allowed the exploitation of some of their possible nanotechnological applications

A construção de sistemas metal-orgânicos supramoleculares através da exploração da conectividade de ligantes terpiridínicos e o desenvolvimento de suas aplicações em nanodispositivos, são tratados nesta tese. Foram desenvolvidos novos complexos de ferro e rutênio com ligantes terpiridínicos funcionalizados, capazes de gerar filmes finos e apresentar interações supramoleculares do tipo hóspede-hospedeiro. Esses complexos foram empregados na modificação de superfícies de dióxido de titânio, visando aplicações em sensores e dispositivos fotoeletroquímicos. Modificando-se o dióxido de titânio nanocristalino, com moléculas hospedeiras de carboxi-metil-β-ciclodextrina, foi possível gerar um sistema seletivo para fotodegradação de compostos aromáticos, como demonstrado para o complexo bis(4\'-(4-bromo-fenil)-2,2\':6\',2\'\'-terpiridina)ferro(II), cujo descoramento foi observado efetuando-se a fotoirradiação no ultravioleta. Esse sistema foi aprimorado para gerar um dosímetro de UV, com base nesse princípio. Além disso, foram feitos estudos de eletropolimerização desse complexo e sobre a capacidade dos filmes moleculares gerados, de atuarem em sensores amperométricos na detecção de espécies químicas relevantes, como os íons nitrito. Outro complexo sintetizado foi o [Ru(c-ph-terpy)(Q)(NCS)], em que c-ph-terpy é a 4\'-(4-carboxi-fenil)-2,2\':6\',2\'\'-terpiridina e Q é o ligante 8-oxiquinolinato. Esse complexo terpiridínico foi desenvolvido para ser utilizado como fotossensibilizador em células solares do tipo Grätzel, tanto na forma direta, como após a modificação da superfície de dióxido de titânio com a carboxi-metil-β-ciclodextrina. Demonstrou-se que através da sua inclusão na cavidade supramolecular, o fotossensibilizador aumenta a eficácia da fotoconversão de energia. Finalmente, foi sintetizada uma nova supermolécula a partir da auto-montagem coordenativa entre a tetra-piridilporfirina e complexos de rutênio(II) coordenados com ligantes oxalato e 4-cloro-2,2\':6\',2\'\'-terpiridina. Foi observado que essa supermolécula apresenta atividade catalítica de oxidação de substratos orgânicos, associada aos grupos periféricos. Os vários sistemas estudados possibilitaram avançar nas estratégias de engenharia supramolecular, através da construção de novos conectores, blocos de montagem e filmes moleculares, bem como avaliar algumas de suas aplicações nanotecnológicas. / This thesis deals with the development of new metal-organic supramolecular systems based on functionalized terpyridine compounds, including their application in nanotechnological devices. New iron and ruthenium coordination compounds incorporating terpyridine ligands have been obtained, and their ability to generate thin films and participate in host-guest interactions has been conveniently explored. Such complexes have been employed in the modification of titanium dioxide surfaces, for applications in sensors and photoeletrochemical cells. By combining nanocrystalline titanium dioxide with carboxy-methyl-β-cyclodextrin, a novel, efficient strategy has been devised for photodegradation of aromatic compounds, and successfully demonstrated after anchoring the bis(4\'-(4-bromophenyl)-2,2\':6\'2\'\'-terpyridine)iron(II) complex and monitoring its bleaching by exposing to UV radiation. In this way, this system has been successfully employed in the design of a novel, versatile UV dosimeter. Electropolymerization studies have also been carried out on this complex, in order to generate molecular films for use in amperometric sensors, capable of probing relevant species, such as the nitrite ions. Another compound dealt with in this work was [Ru(c-ph-terpy)(Q)(NCS)], where c-ph-terpy = 4\'-(4-carboxy-pheny)-2,2\':6\',2\'\'-terpyridine, and Q = 8-oxyquinolinate ligand. This terpyridine complex has been designed as fotosensitizer in Grätzel\'s photoelectrochemical cells, by its direct coating on the titanium dioxide nanoparticles or by performing their previous treatment with carboxi-methyl-β-cyclodextrin. It has been shown that the inclusion into the cyclodextrin cavity improves the performance of the photosensitizer for energy conversion. Finally, a new supermolecule encompassing a central tetrapyridylporphyrin unity attached to four chloro(oxalate)(4-chloro-2,2\':6\',2\'\'-terpyridine)ruthenium(II) complexes, has been synthesized. This species exhibits catalytic activity in the oxidation of organic compounds. The reported study, involving several systems, has contributed to the available molecular engineering strategies, through the building up of new connecting groups and molecular films, and has also allowed the exploitation of some of their possible nanotechnological applications

Metaloporfirinas que incorporam complexos ligados ao anel macrocíclico podem apresentar efeitos supramoleculare, mimetizando, por exemplo, sistemas fotossintéticos, em relação à capacidade de promover transferência eletrônica intramolecular fotoinduzida, e a enzima citocromo-c oxidase, em seu papel de catalisador multieletrônico na redução do oxigênio molecular. Em vista desta potencialidade, demos início ao estudo de uma nova série de porfirinas polinucleares derivadas da mesotetra(4-piridil)porfina, [4-TPyPJ, por meio da complexação dos resíduos de piridina com íons pentaaminrutênia ou etilenodiaminatetraacetato(rutenato). Porfirinas com três íons pentaaminrutênio e quatro íons Ru(edta) ligados às piridinas foram isolados e caracterizados, por meio de técnicas espectroscópicas e eletroquímicas. O espectro eletrônico dos complexos apresenta as bandas Soret, α e β características, na região do visíveL. Nas espécies reduzidas foi observada uma nova banda, consistente com a transição de transferência de carga RuII---› py, na faixa de 440-470 nm. Os estudos por meio de voltametria cíclica proporcionaram evidências diretas da ligação dos complexos de rutênio às piridinas. As ondas reversíveis observadas estão deslocadas anodicamente com relação ao potenciaL redox do aquo complexo. Foi estudado, também, o comportamento eletroquímico das porfirinas polimetaladas na presença de dimetilsulfóxido, o quaL é um sequestrante de íons [Ru(edta)(H2 O)] . Na presença de oxigênio molecular, foi observada uma intensa onda catalítica no voltamograma cíclico da ferro porfirina polimetalada, sendo a mesma quase coincidente com o potencial de redução do íon ferro. O comportamento eletroquímico é consistente com a redução do dioxigênio à água. Esta reação é auxiliada pelos quatro complexos de rutênio periféricos, os quais agem como fonte de elétrons , melhorando a eficiência catalítica por meio de interações supramoleculares. / Metalloporphyrins containing peripheral meta l complexes attached to the macrocyclic ring can exhibit an interesting supramolecular chemistry, modeling , for instance, photosynthetic systems in their ability to undergo intramolecular photocatalyzed electron transfer; and cytochrome-c oxidase , by acting as multielectron redox catalysts in the reduction of molecular oxygen. In view of its relevance , we have investigated a new series of polynuclear porphyrins derived from meso-tetra(4-pyridyl)porphyrin , [4-TPyP], by complexing the pyridine residues with ruthenium-ammines or ruthenium-EDTA íons. Typical species , containing three pentaammineruthenium (III) or four EDTA-ruthenium(III) ions attached to the porphyrin , were isolated and characterized based on spectroscopic and electrochemical techniques. The electronic spectra exhibited the characteristic Soret , α and β bands in the visible region. In the reduced species a new band , consistent with a Ru(II)-to-pyridine charge transfer transition , was detected in the 440-470 nm region. Cyclic voltammetry measuremen ts provided direct evidence of the attached ruthenium ions, displaying reversible waves, slightly shifted to less cathodic potentials with respect to the non-coordinated species. The electrochemical behaviour was also investigated in the presence of dimethyl sulfoxide , wich is a scavenger for RuII (edta)(H2 O) complex. In the presence of dioxygen, a strong catalytic wave was observed for the polymetallated iron-porphyrin , almost coinciding with the electrachemical wave for the iron centre. The electrochemical behaviour was consistent with the reduction of dioxygen to water, at the iron-porphyrin centre. The process is assisted by the four ruthenium(II) ions which act as a source of electrons, improving the catalytic efficiency by means of the supramolecular interactions.

Wang, Minji. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references (leaves 91-97). / Abstracts in English and Chinese. / Acknowledgement --- p.i / Abstract --- p.ii / 摘要 --- p.iii / Chapter Chapter 1. --- Introduction --- p.1 / Chapter 1.1 --- Weak Intermolecular Interactions --- p.1 / Chapter 1.1.1 --- Van der Waals Interaction --- p.1 / Chapter 1.1.2 --- Hydrogen Bonds --- p.2 / Chapter 1.1.3 --- π…π Interactions --- p.4 / Chapter 1.1.4 --- Lone-Pair…Aromatic Interactions --- p.5 / Chapter 1.1.5 --- Halogen…Halogen Interactions --- p.6 / Chapter 1.2 --- Argentophilic Interaction --- p.7 / Chapter 1.3 --- Silver Acetylenediide and Silver Arylethynide --- p.11 / Chapter 1.3.1 --- "C2@Agn(n = 6, 7, 8, 9, 10)" --- p.11 / Chapter 1.3.2 --- "Ag4eC=C-C=Cz>Ag4 and R-C=C@=)Agn, (n = 4, 5; R = Aryl, t-Bu)" --- p.12 / Chapter 1.4 --- Research Strategy --- p.14 / Chapter Chapter 2. --- "Coordination Networks Constructed with the Supramolecular Synthon System Rx-CsCzAgn (n = 4,5; Rx = halophenyl)" --- p.16 / Chapter 2.1 --- Crystal Structure of AgC=CC6H4l-4 ´Ø 2AgCF3COO (2.1) --- p.17 / Chapter 2.2 --- Crystal Structure of AgC=CC6H4l-4 . 3AgNO3 (2.2) --- p.20 / Chapter 2.3 --- "Crystal Structure of 2AgC=CC6H3Cl2-3,4 . 5AgCF3COO ´Ø 2CH3CN . H20 (2.3)" --- p.25 / Chapter 2.4 --- Crystal Structure of 4AgC=CC6H4Cl-3 . 6AgC2F5COO ´Ø 5CH3CN (2.4) & 4AgOCC6H4Br-3 ´Ø 6AgC2F5COO ´Ø 5CH3CN (2.5) --- p.28 / Chapter 2.5 --- Crystal Structure of 2AgC=CC6H4Cl-2 . 4AgCF3COO ´Ø NC(CH2)4CN (2.6) & 2AgOCC6H4Cl-2 ´Ø 4AgCF3COO ´Ø 2CH3CN (2.7) --- p.32 / Chapter 2.6 --- Crystal Structure of AgC=CC6H4F-2 ´Ø 2CF2(CF2COOAg)2 ´Ø 2CH3CN (2.8) --- p.36 / Chapter 2.7 --- Crystal Structure of 4AgC=CC6H4N02-2 ´Ø 10AgC3F7COO ´Ø 4CH3CN . 4H20 (2.9) --- p.39 / Chapter 2.8 --- Summary --- p.41 / Chapter Chapter 3. --- Network Assembly with the Supramolecular Synthon System Rx-C=C3Agw (/i = 3 to 5; Rx = nitrophenyl) --- p.43 / Chapter 3.1 --- Crystal Structure of AgC=CC6H4N02-2 ´Ø 3AgC2F5COO . 2CH3CN (3.1) --- p.44 / Chapter 3.2 --- Crystal Structure of AgC=CC6H4N02-4 ´Ø 3AgC2F5COO ´Ø CH3CN (3.2) --- p.47 / Chapter 3.3 --- Crystal Structure of AgC=CC6H4N02-4 ´Ø 4AgCF3COO ´Ø 2CH3CN (3.3) --- p.50 / Chapter 3.4 --- Crystal Structure of AgC=CC6H4N02-4 ´Ø 3AgCF3COO . CH3CN ´Ø 0.5NC(CH2)4CN (3.4) --- p.53 / Chapter 3.5 --- Crystal Structure of AgC=CC6H4N02-4 ´Ø 3AgC2F5COO ´Ø 2CH3CN (3.5) --- p.56 / Chapter 3.6 --- Crystal Structure of AgC=CC6H4N02-4 ´Ø 3AgC2F5COO ´Ø CH3CN ´Ø NC(CH2)4CN (3.6) --- p.59 / Chapter 3.7 --- Crystal Structure of 4AgC三CC6H4NOr4 ´Ø 4AgC3F7COO ´Ø 3CH3CN (3.7) --- p.62 / Chapter 3.8 --- Crystal Structure of 3AgC=CC6H4N02-4 ´Ø 3AgCF3COO ´Ø 3CH3CN (3.8) --- p.66 / Chapter 3.9 --- Crystal Structure of 7AgC三CC6H4NOr4 ´Ø 17AgCF3COO ´Ø 11CH3CN ´Ø H20 (3.9) --- p.68 / Chapter 3.10 --- Crystal Structure of AgC=CC6H4N02-4 ´Ø CF2(CF2COOAg)2. AgCFsCOO . H2O (3.10) --- p.72 / Chapter 3.11 --- Summary --- p.76 / Chapter 3.12 --- Further Development --- p.77 / Chapter 3.12.1 --- Elongation of Ethynide Ligands --- p.77 / Chapter 3.12.2 --- Incorporating More Ethynide Ligands into One Compound --- p.78 / Chapter Chapter 4. --- Experimental --- p.79 / Chapter 4.1 --- Synthesis --- p.79 / Chapter 4.2 --- X-Ray Crystallography --- p.84 / References --- p.91

Yau, Chung Wah. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2007. / Includes bibliographical references (leaves 55-57). / Abstracts in English and Chinese. / Acknowledgement --- p.i / Abstract --- p.ii / Table of Contents --- p.iv / Index of Compounds --- p.v / Chapter 1. --- Introduction / Chapter 1.1 --- Fundamentals of inclusion chemistry --- p.1 / Chapter 1.2 --- Hydrogen bonding in supramolecular chemistry and crystal engineering --- p.3 / Chapter 1.3 --- Hydrogen-bonded rosette system --- p.4 / Chapter 1.4 --- Research plan --- p.7 / Chapter 2. --- Descriptions of crystal structures / Chapter 2.1 --- Supramolecular rosette layer and rosette ribbon constructed from guanidinium cations and hydrogen carbonate dimers /carbonate anions / Chapter 2.1.1 --- (Et4N+)[C(NH2)3+]7(C032-)3[C3N2H2(C00-)2] (1) --- p.11 / Chapter 2.1.2 --- [(n-Bu)4N+]3[C(NH2)3+]4(HC03-)4[H+{C3N2H-(C00-)(C00H)}2] (2) --- p.14 / Chapter 2.1.3 --- [(n-Bu)4N+]2[C(NH2)3+]2(HC03-)2[NCC6H4(C00-)]2 ´Ø 2H20 (3)…… --- p.16 / Chapter 2.1.4 --- "[(n-Bu)4+]8[C(NH2)3+]8(HCO3-)8[4,4'-C12H8(C00-)2]4 ´Ø 8H20 ´″…" --- p.17 / Chapter 2.2 --- Channel- and layer-type anionic host structures constructed from benzene hexacarboxylic acid and guanidinium cation / Chapter 2.2.1 --- [C6(COO-)6][C(NH2)3]6 ´Ø H20 (5) --- p.20 / Chapter 2.2.2 --- [C6(COOH)3(COO´ؤ)3][C(NH2)3+]3 ´Ø 2H20 (6) --- p.23 / Chapter 2.2.3 --- [(n-Pr)4N+][C6(COOH)5(COO-)] ´Ø 3H20 (7) --- p.27 / Chapter 2.2.4 --- [(n-Bu)4N+]4[C6(COOH)5(COO-)]2[C6(COOH)4(COO-)2]2 [C(NH2)3+]2.8H2O(8) --- p.30 / Chapter 2.2.5 --- (Et4N+)2[C6(COOH)4(COO-)2]2[C(NH2)3+]2 ´Ø 2H20 (9) --- p.35 / Chapter 2.2.6 --- (Me4N+)[C6(COOH)3(COO-)3][C(NH2)3+]2 ´Ø H20 (10) --- p.37 / Chapter 3. --- Summary and discussion / Chapter 3.1 --- Robustness of hydrogen-bonded supramolecular rosette networks --- p.40 / Chapter 3.2 --- Versatile hydrogen bonding modes of guanidinium with mellitate anions --- p.43 / Chapter 4. --- Experimental / Chapter 4.1 --- Preparation methods --- p.48 / Chapter 4.2 --- X-ray crystallography --- p.52 / Chapter 5. --- References --- p.55 / "Appendix A: Tables of atomic coordinates, thermal parameters, bond lengths and angles and hydrogen bonds" --- p.58

Crystal engineering is a rapidly developing area of research with goals aimed at designing molecular solids with desired physical and chemical properties. By utilizing reliable intermolecular interactions, the principles of supramolecular chemistry are exploited in the solid state in order to achieve favorable arrangements of molecules in a crystal lattice. We have applied crystal engineering strategies to further develop the strategy of template-directed reactivity in the solid state. An evaluation of catechol, a regioisomer of the commonly used resorcinol template, was performed. Co-crystallization of the template candidate with a bis-pyridyl olefin produced a discrete self-assembled architecture wherein hydrogen-bonded dimers of catechol pre-organize the olefins for a [2+2] photodimerization in the solid state. The dimerization was determined to proceed quantitatively and X-ray studies of a partial single-crystal-to-single-crystal reaction supported the hypothesis of the reaction proceeding exclusively within the discrete assemblies, despite the infinite stacking of the olefins. A study of substituent effects on the conformational bias of additional catechol- based template candidates was carried out. Candidates with bulky substituents a the 3- and 4-positions were observed to adopt a favorable syn-anti or syn-gauche conformer in most cases. Though conformational bias was induced and discrete assembly achieved, only one of the synthesized cocrystals met the geometric requirements for a photodimerization, however, extended UV exposure produced no evidence of product formation. We discuss the fortuitous discovery of a catechol-based cocrystal system that produces an infinite linear assembly. The fluorine atom of 3-fluorocatechol was observed to be too small to induce conformational bias in the template candidate. However, the system was observed to progress through a three-step solvent-mediated phase transformation. The second and third crystal phases were isolated and characterized by single-crystal X-ray diffraction. The X-ray data revealed that the zig-zag assembly of the first phase spontaneously transforms to a double helix topology in the second phase, before transforming to the final phase, which exhibits a quadruple helix topology. In our studies of pharmaceutical cocrystals, we sought to perform a systematic study of the solid-state behavior of the anti-cancer drug 5-fluorouracil. Inspired by previously published cocrystal structures, we performed co-crystallization experiments with a small series of structurally similar coformers. Comparison of the three structures revealed an inconsistent degree of synthon disruption between the coformers. Curiously, one of the cocrystals obtained displayed a packing arrangement consistent with the requirements of a [2+2] cycloaddition. Irradiation of the sample with UV light resulted in the quantitative formation of a cross-photocycloaddition product. The product was characterized as a pyrimidine-fused cyclobutane, the first reported synthetic derivative of 5-fluorouracil obtained from a solid-state reaction. Lastly, we utilize crystal engineering strategies to study the behavior of 2- iodohippuric acid, a common radio-imaging target. The pharmacokinetic properties of 2- iodohippuric acid make it an ideal target for renal imaging. We sought to approach a solid formulation of the target in a similar manner to that of a drug or other metabolized pharmaceutical. In doing so, we hoped to study the compound’s behavior in the solid state so that we may eventually use co-crystallization as a means of altering the properties of the target for the purpose of generalizing its use in imaging the body.

Abstract not available