Este trabalho consiste no estudo de complexos de Ni(II) com dialquilsulfóxidos. Os compostos foram sintetizados e caracterizados através de espectroscopia vibracional e eletrônica, medidas magnéticas e de condutância e determinação de ponto de fusão. Obtiveram-se os seguintes complexos: [Ni(R2SO)6](ClO4)2 (R = Me, n-Pr, n-Bu e i-Bu); [Ni (Me2SO)6] (NO3)2; [Ni (Me2SO)4 (NO3)](NO3); [Ni(R2SO)3 (NO3)2] (R = Me2SO, Me2SO-d6, n-Bu e i-Bu) e [Ni(R2SO)2 (N03)2] (R = n-Pr, i-Bu e t-Bu). O método de síntese é crítico para a obtenção de compostos bem definidos, principalmente no caso dos nitratos onde existe a possibilidade de formação de compostos de diferentes estequiometrias para o mesmo sulfóxido. Os complexos [Ni(Me2SO)6] (Cl04)2 e [Ni(Me2SO)4 NO3] NO3 não fundem até 245° C. Os demais fundem em temperaturas relativamente baixas. Alguns complexos de nitrato apresentam grandes intervalos de fusão, que podem ser devidos a perdas de ligante. Os complexos são octaédricos com os sulfôxidos coordenados ao Ni(II) através do átomo de oxigênio, conforme evidenciado por medidas magnéticas e espectroscopia vibracional e eletrônica. A influência doânion é marcante. O grupo perclorato não se coordena ao íon metálico, enquanto que o grupo nitrato pode não se coordenar ou, então, atuar como ligante monodentado ou bidentado, competindo com o sulfóxido na primeira esfera de coordenação do Ni(II). Os complexos contendo perclorato comportam-se como eletrólitos do tipo 1:2 em nitrometano. Os compostos contendo nitrato, ao contrário, comportam-se todos como nao condutores no mesmo solvente, embora os sólidos de Me2SO com proporção molar níquel-sulfóxido 1:6 e 1:4 apresentem nitrato iônico. Isto é uma evidência de que as espécies em solução não são as mesmas presentes nos sólidos. Os espectros eletrônicos confirmam este fato. As diferenças de basicidade e estereoquímica dos sulfóxidos afetam pouco os valores de Dq e B dos complexos contendo perclorato. Portanto, os sulfóxidos di-propílico e di-butílicos estudados ocupam a mesma posição do Me2SO na série espectroquímica e, também, na série nefelauxética. / This work consists on the study of Ni(II) complexes with dialquilsulfoxides. The compounds were synthesized and characterized by vibrational and electronic spectroscopies, magnetic and conductance measurements and melting point determination. The following complexes were obtained: [Ni(R2SO)6](ClO4)2 (R = Me, n-Pr, n-Bu and i-Bu); [Ni (Me2SO)6] (NO3)2; [Ni (Me2SO)4 (NO3)] NO3; [Ni(R2SO)3 (NO3)2] (R = Me2, Me2SO-d6, n-Bu and i-Bu) and [Ni(R2SO)2 (NO3)2] (R = n-Pr, i-Bu and t-Bu). The synthetic procedure is critical for the preparation of well defined compounds, mainly for the nitrates where the possibility of formation of compounds with different stoichiometry for the same sulfoxide exists. The complexes [Ni (Me2SO 6] (ClO4)2 and [Ni (Me2SO)4 NO3] NO3 do not melt up to 245°C, and the others melt at relatively low temperatures. Some nitrate complexes show broad melting point ranges, which may be due to ligand loss during the heating. The complexes are octahedral, and have the sulfoxides coordinated to the Ni(II) through the oxygen atom, as shown by magnetic measurements and the vibrational and electronic spectra. The anion influence is very important. The perchlorate group does not coordinate to the metal ion, while the nitrate group may either be non coordinating or behave as a monodentate or bidentate ligand, competing with the sulfoxide for the first coordination sphere of Ni(II). The perchlorate complexes are l:2 type electrolytes in nitromethane solution. The nitrate complexes, on the other hand, are non conducting in the same solvent, although the solid compounds of Me2SO which have molar Ni: sulfoxide ratios of l:6 and l:4 possess ionic nitrate in their molecules. This is an evidence of the existence of different species in the solid state and in solution in these cases. The electronic spectra confirm this fact. The differences in the basicity and in the stereochemistry of the sulfoxides affect little the Dq and B values in the perchlorate complexes. This implies the di-propyl and di-butylsulfoxide studied fall in the same position as the dimethylsulfoxide in the spectrochemical and nephelauxetic series.

Incorporation of heteroaromatic rings (pyridyl, pyrazinyl, pyrimidyl and thienyl) in the silver-ethynide supramolecular synthon led to a series of silver(I) double salts of various heterocyclic ethynide ligands. Through variation of the relative orientations between the ethynide moiety and heteroatom as well as between heteroatoms, different coordination networks were generated. / Synthetic and structural studies were carried out on a series of silver(I) complexes of phenylethynide and phenylethynide derivatives with alkyl substituents (methyl, tert- butyl, trifluoromethyl) at variable positions (p-, m-, o-) on the aromatic ring. The invariable appearance of the mu4- and mu5-ligation modes of the ethynide moiety in ten silver(I) complexes reaffirms the general utility of the silver-arylethynide supramolecular synthon Ar-C≡C⊃Agn( n = 4, 5) in coordination network assembly. / Systematic investigation on silver(I) tert-butylethynide complexes resulted in the establishment of the general utility of the silver-ethynide supramolecular synthon with an alkyl tail. Upon the addition of nitrile ligands from CH3CN, CH3CH2CN to (CH3) 3CCN, adjacent silver ethynide moieties tBu-C≡C⊃Ag 5 approach closer to each other, and the resulting crystal structure transforms from a 2-D hydrogen bonding network, through a 2-D network held by hydrogen bonding and coordination, to a 2-D coordination network. Employment of the multidentate dicarboxylate ligand O2CCF2CF 2CO2 and the dinitrile ligand NC(CH2)4CN led to the formation of higher-dimensional networks. / The above-mentioned structural studies of silver-ethynide complexes of aromatic or heteroaromatic ligands indicate that pi-pi stacking plays a pivotal role in the self-assembly of corresponding silver-ethynide synthons. Investigation of the silver(I) complexes of phenylethynide and its derivatives with different substituents (methyl, tert- butyl) in variable positions (o-, m-, p-) on the aromatic ring shows the relative position and the bulk of substituents both affect the pi-pi stacking between adjacent phenyl rings. Furthermore, a comparative study of pi-pi stacking in the nitrate complexes Ag2(m-C≡CC 6H4C≡C)] · 5AgNO3 · 3H 2O (38), [(3-AgC≡C)-py] · 3AgNO3 (45), 2[(2-AgC≡C)-pyraz] · 6AgNO3 3H 2O (50) and 2[2,3-(AgC≡C)2-thienyl] · 10AgNO3 (56) suggests that the pi-electron deficiency of the aromatic ring also weakens this non-covalent interaction. (Abstract shortened by UMI.) / The ensuing study of silver(I) phenylenediethynide complexes led to the recognition of another kind of supramolecular synthon, Agn⊂ C2---R---C2⊃Agn (R= p-, m-, o-C6H4; n = 4, 5). / The reaction of Li-C≡C-Ca≡C-Li (generated in situ from hexachloro-1,3-butadiene and nBuLi) with AgNO3 led to the generation of a new silver carbide, silver 1,3-butadiynediide (Ag2C4). A series of fifteen double and multiple salts of Ag2C4 were synthesized by dissolving this polymeric starting material Ag2C4 in a concentrated aqueous solution of soluble silver salts (e.g. AgNO3, AgCF 3CO2, AgC2F5CO2). The silver-ethynide interaction may be conceived as a new kind of supramolecular synthon for the construction of 1-D, 2-D and 3-D coordination polymers. The terminal silver-ethynide interactions that are assigned in diverse configurations can be conveniently classified into three types: sigma, pi and mixed (sigma,pi), and tuned by variation of ancillary anionic ligands. In addition, the controlled hydrolysis of hexafluorophosphate led to the generation of the second silver quadruple salt Ag2C4 · 4AgNO3 · AgPF 2O2 · Ag3PO4 (4). The (F)2(H2O)18 fluoride-water tape in Ag 2C4 · 2AgF · 10AgC2F5CO 2 · CH3CN · 12H2O (10) and the (C4)3 Ag18 aggregate in 3Ag 2C4 · 12AgC2F5CO2 · 5[BzMe3N)C2F5CO2] · 4H 2O (15) are both unprecedented among silver(I)complexes. / This thesis describes our effort to explore, develop and utilize the silver-ethynide interaction in new kinds of metal-ligand supramolecular synthons for the construction of silver(I) coordination networks. / Zhao, Liang. / Adviser: Thomas C. W. Mak. / Includes supplementary digital materials. / Source: Dissertation Abstracts International, Volume: 69-02, Section: B, page: 1011. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2007. / Includes bibliographical references (leaves 208-228). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese. / School code: 1307.

Ku, Ka Wai. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2011. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese.

by Xiao-Ming Chen. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1992. / Includes bibliographical references (leaves 127-135). / Acknowledgements / Abstract --- p.i / Nomenclature --- p.ii / Table of Contents --- p.iii / List of Tables --- p.iv-v / List of Figures --- p.v-vii / Chapter 1. --- Introduction --- p.1-9 / Chapter 2. --- Results and Discussion --- p.10-104 / Chapter 1. --- Betaine derivatives --- p.10-19 / Chapter 2. --- "Complexes of manganese(II), cobalt(II), and nickel(II)" --- p.20-31 / Chapter 3. --- Complexes of zinc(II) --- p.32-40 / Chapter 4. --- Complexes of cadmium(II) and mercury(II) --- p.41-56 / Chapter 5. --- Complexes of silver(I) --- p.57-76 / Chapter 6. --- Complexes of copper(II) --- p.77-97 / Chapter 7. --- Mixed-metal complexes --- p.98-104 / Chapter 3. --- Conclusions --- p.105-106 / Chapter 4. --- Experimental --- p.107-126 / Chapter 5. --- References --- p.127-135 / Chapter 6. --- Appendix A --- p.136-151 / Chapter 1. --- Atomic coordinates and equivalent isotropic thermal parameters --- p.136-144 / Chapter 2. --- Anisotropic thermal parameters --- p.145-151 / Chapter 7. --- Appendix B (in a separated volume to be kept as Supplementary Data in the Department of Chemistry) Tables of structure factors

Hu, Ting. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2013. / Includes bibliographical references (leaves 185-198). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese.

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

The work presented in this thesis deals with the employment of Schiff base ligands used to synthesise novel 3d-4f polynuclear coordination clusters (PCCs) and the investigation into their potential magnetic, luminescent and catalytic properties. Chapter one provides a general introduction to the chemistry described in the thesis. It includes a general overview of 3d-4f PCC chemistry and the applications of these materials and previous synthetic strategies for the preparation of Schiff base PCCs. A rationale is presented for the ligands employed in the thesis and a synthetic strategy is devised for the synthesis of specific materials. The initial chapters are focused on the synthesis of 3d-4f PCCs with novel core topologies and the study of their magnetic properties. Several novel series of 3d-4f PCCs are presented with unique core topologies which are previously unobserved in 3d-4f PCC chemistry. In addition, some of the presented PCCs display single-molecule magnet (SMM) properties or a significant magnetocaloric effect (MCE). Chapter five bridges synthetic aspects discussed in the previous chapters, with a synthetic study targeting 3d-4f PCCs with a defect dicubane core (2,3M4-1) and introduces the term “isoskeletal” to describe PCCs which possess the same topology or related organic structures with the same host framework but different guests. Chapters seven to nine are focused on the development of a well characterised isoskeletal family of 3d-4f PCCs with a defect dicubane core and the investigation of their potential catalytic properties in a range of organic reactions including Michael Addition, Friedel-Crafts alkylations and multicomponent reactions. Characterisation of the 3d-4f PCCs is emphasised and verifies the stability of the 2,3M4-1 core in solution. An attempt at understanding the catalytic system and mechanistic aspects is undertaken, which is not explored in previously reported 3d-4f PCC co-operative catalysis. Chapter ten provides an overall conclusion to the work presented in the thesis, whilst highlighting the contributions of this work to the reported literature.

by Ka-yue Chiu. / The "3" in the title is subscript. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1996. / Includes bibliographical references (leaves 103-110). / ACKNOWLEDGEMENTS --- p.3 / ABBREVIATIONS --- p.4 / ABSTRACT --- p.5 / Chapter I. --- COORDINATION CHEMISTRY OF SmI3 WITH DONOR SOLVENTS --- p.7 / Chapter 1.1. --- Introduction --- p.7 / Chapter 1.2 --- Results and Discussion --- p.21 / Chapter 1.2.A --- Synthesis and Structural Characterization of [trans-SmI2(THF)5][trans- SmI4(THF)2] (1) --- p.21 / Chapter 1.2.B --- Synthesis and Structural Characterization of SmI3(DME)2 (2) --- p.26 / Chapter 1.2.C --- Synthesis and Structural Characterization of [{Sm(H20)3}2{Sm(CH3CN) (H20)3}2{Sm(CH3CN)3(H20)}2(μ3-OH)8(μ6-0)]I8-2H20 (3) --- p.30 / Chapter 1.3 --- Conclusion --- p.38 / Chapter 1.4 --- Experimental Section --- p.39 / Chapter II. --- SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF LANTHANACARBORANES --- p.45 / Chapter II.1 --- Introduction --- p.45 / Chapter II.2 --- Results and Discussion --- p.51 / Chapter II.2.A --- Synthesis and Characterization of closo-Lanthanacarboranes --- p.51 / Chapter II.2.A.i --- Sandwich Type Complexes --- p.51 / Chapter II.2.A.ii. --- Half-Sandwich Type Complexes --- p.62 / Chapter II.2.B --- Synthesis and Characterization of an exo-nido-Samaracarborane --- p.71 / Chapter II.2.B.i. --- Synthesis and Characterization of an exo-nido-[{(C6H5CH2)2C2B9H9} Sm(DME)2]2.DME(18) --- p.77 / Chapter II.3 --- Conclusion --- p.84 / Chapter II.4 --- Experimental Section --- p.85 / REFERENCES --- p.99

Este trabalho consiste no estudo de complexos de Ni(II) com dialquilsulfóxidos. Os compostos foram sintetizados e caracterizados através de espectroscopia vibracional e eletrônica, medidas magnéticas e de condutância e determinação de ponto de fusão. Obtiveram-se os seguintes complexos: [Ni(R2SO)6](ClO4)2 (R = Me, n-Pr, n-Bu e i-Bu); [Ni (Me2SO)6] (NO3)2; [Ni (Me2SO)4 (NO3)](NO3); [Ni(R2SO)3 (NO3)2] (R = Me2SO, Me2SO-d6, n-Bu e i-Bu) e [Ni(R2SO)2 (N03)2] (R = n-Pr, i-Bu e t-Bu). O método de síntese é crítico para a obtenção de compostos bem definidos, principalmente no caso dos nitratos onde existe a possibilidade de formação de compostos de diferentes estequiometrias para o mesmo sulfóxido. Os complexos [Ni(Me2SO)6] (Cl04)2 e [Ni(Me2SO)4 NO3] NO3 não fundem até 245° C. Os demais fundem em temperaturas relativamente baixas. Alguns complexos de nitrato apresentam grandes intervalos de fusão, que podem ser devidos a perdas de ligante. Os complexos são octaédricos com os sulfôxidos coordenados ao Ni(II) através do átomo de oxigênio, conforme evidenciado por medidas magnéticas e espectroscopia vibracional e eletrônica. A influência doânion é marcante. O grupo perclorato não se coordena ao íon metálico, enquanto que o grupo nitrato pode não se coordenar ou, então, atuar como ligante monodentado ou bidentado, competindo com o sulfóxido na primeira esfera de coordenação do Ni(II). Os complexos contendo perclorato comportam-se como eletrólitos do tipo 1:2 em nitrometano. Os compostos contendo nitrato, ao contrário, comportam-se todos como nao condutores no mesmo solvente, embora os sólidos de Me2SO com proporção molar níquel-sulfóxido 1:6 e 1:4 apresentem nitrato iônico. Isto é uma evidência de que as espécies em solução não são as mesmas presentes nos sólidos. Os espectros eletrônicos confirmam este fato. As diferenças de basicidade e estereoquímica dos sulfóxidos afetam pouco os valores de Dq e B dos complexos contendo perclorato. Portanto, os sulfóxidos di-propílico e di-butílicos estudados ocupam a mesma posição do Me2SO na série espectroquímica e, também, na série nefelauxética. / This work consists on the study of Ni(II) complexes with dialquilsulfoxides. The compounds were synthesized and characterized by vibrational and electronic spectroscopies, magnetic and conductance measurements and melting point determination. The following complexes were obtained: [Ni(R2SO)6](ClO4)2 (R = Me, n-Pr, n-Bu and i-Bu); [Ni (Me2SO)6] (NO3)2; [Ni (Me2SO)4 (NO3)] NO3; [Ni(R2SO)3 (NO3)2] (R = Me2, Me2SO-d6, n-Bu and i-Bu) and [Ni(R2SO)2 (NO3)2] (R = n-Pr, i-Bu and t-Bu). The synthetic procedure is critical for the preparation of well defined compounds, mainly for the nitrates where the possibility of formation of compounds with different stoichiometry for the same sulfoxide exists. The complexes [Ni (Me2SO 6] (ClO4)2 and [Ni (Me2SO)4 NO3] NO3 do not melt up to 245°C, and the others melt at relatively low temperatures. Some nitrate complexes show broad melting point ranges, which may be due to ligand loss during the heating. The complexes are octahedral, and have the sulfoxides coordinated to the Ni(II) through the oxygen atom, as shown by magnetic measurements and the vibrational and electronic spectra. The anion influence is very important. The perchlorate group does not coordinate to the metal ion, while the nitrate group may either be non coordinating or behave as a monodentate or bidentate ligand, competing with the sulfoxide for the first coordination sphere of Ni(II). The perchlorate complexes are l:2 type electrolytes in nitromethane solution. The nitrate complexes, on the other hand, are non conducting in the same solvent, although the solid compounds of Me2SO which have molar Ni: sulfoxide ratios of l:6 and l:4 possess ionic nitrate in their molecules. This is an evidence of the existence of different species in the solid state and in solution in these cases. The electronic spectra confirm this fact. The differences in the basicity and in the stereochemistry of the sulfoxides affect little the Dq and B values in the perchlorate complexes. This implies the di-propyl and di-butylsulfoxide studied fall in the same position as the dimethylsulfoxide in the spectrochemical and nephelauxetic series.

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