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Structure and Properties of Self-Assembled Coordination Compounds: Homoleptic D10-Metal Aryl/Alkylacetylides, Ruthenium N-Heterocycles and Picolinates(English)

Structure and Properties of Self-Assembled Coordination Compounds: Homoleptic D10-Metal Aryl/Alkylacetylides, Ruthenium N-Heterocycles and Picolinates(English)

          
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About the Book

This dissertation, "Structure and properties of self-assembled coordination compounds: homoleptic d10-metal aryl/alkylacetylides, ruthenium n-heterocycles and picolinates" by Fei-yeung, Ng, 吳飛洋, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. Abstract: Abstract of thesis entitled STRUCTURE AND PROPERTIES OF SELF-ASSEMBLED COORDINATION COMPOUNDS: 10 HOMOLEPTIC d -METAL ARYL/ALKYLACETYLIDES, RUTHENIUM N-HETEROCYCLES AND PICOLINATES Submitted by Ng Fei Yeung for the degree of Doctor of Philosophy at The University of Hong Kong in October 2006 Polymeric homoleptic metal complexes are novel materials with practical applications. Due to their low solubility in common solvents, determination of their structures is a difficult task. In this work, the structures of 10 t homoleptic d metal-aryl/alkylacetylide polymer [R-C≡C-M] (M = Cu, R = Bu 1, Ph 2; R = Ph, M = Ag 3; Au 4, M = Cu, R = C H, n = 3 5, 4 6, 6 7, 8 8, 10 9, n 2n+1 16 10; R = cyclohexyl 11) and ruthenium μ-oxo pyrazolate Ru (O)(Hpz) (pz) 12 2 4 4 (Hpz = pyrazole) were determined by single crystal X-ray and X-ray powder diffraction (PXRD) measurements. 1-C H features an unusual Cu catenane 6 6 20 cluster structure possessing various types of BuC≡C→Cu coordination modes. This single crystal structure acted as a starting model for subsequent Rietveld refinement of X-ray powder diffraction data. The structures of the polycrystalline [M-C≡C-Ar] and [Cu-C≡C-R] have been studied by PXRD and powder small angle X-ray scattering (SAXS) techniques. Compound 2 exhibits an infinite chain structure with extended Cu-Cu ladders (Cu-Cu = 2.49(4)-2.83(2) A). The silver(I) congener 3 is iso-structural to 2 (average Ag-Ag distance = 3.11 A) whereas the gold(I) analog 4 shows a Au---Au honeycomb network with PhC≡C pillars (Au-Au = 2.98(1)-3.26(1) A). 5 and 9 have extended sheet structure with zig-zag Cu subunits connected by bridging acetylides (Cu-Cu = 2.44-2.61 A and 2.45-2.82 A respectively). 6 displays a herringbone structure (Cu-Cu = 2.39-2.86 A). 7 shows a 1-dimensional infinite chain (Cu-Cu = 2.24-2.42 A). Polymorphism was found for the 9 and 10 crystalline solids as studied by SAXS, which revealed low-angle reflections (2θ) at 2.3-2.86 for 9 polymorphs and 1.81-2.48 for 10 polymorphs. Variable-temperature PXRD (VT-PXRD) showed that these n-alkylacetylides underwent lattice expansion at elevated temperature before decomposition. Low-temperature VT-PXRD of 6 confirmed lattice contraction in [ 01] 1 for ca. 0.4 (2θ). Compounds 1-4 and 5-10 show a strong yellow to red emission in solid state. Solution-state absorption and luminescent properties of 6-10 were also studied and revealed fluorescent photoluminescent properties of the compounds. 10 The physical and spectroscopic properties of all d metal-aryl/alkylacetylides were discussed in accordance to their structures. The reaction between Ru (OAc)Cl and pyrazole produced a 2 4 self-assembled μ-oxo bridged diruthenium pyrazolate Ru (O)(Hpz) (pz) 12 with 2 4 4 pyrazoles in different coordination modes. The crystal structure of 12 displays III, III unprecedented columnar zeolitic structure with Ru---Ru = 3.190 A. This Ru 2complexes showed intense absorption band at 589 nm attributed to the transition between d(Ru) and p(O) levels. Hydrothermal/solvothermal syntheses π π produced three more ruthenium N-donor complxes [Ru(Hpz) Cl ]Cl 13, 4 2 H[RuCl (6-Me-pic) ] 14 (6-Me-pic = 6-methylpicolinate) and 2 2 K[RuCl (5-COOH-pic) ] 15 (5-COOH-pic = pyridine-2,5-dicarboxylic acid), 2 2 whose struct


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Product Details
  • ISBN-13: 9781361427361
  • Publisher: Open Dissertation Press
  • Publisher Imprint: Open Dissertation Press
  • Height: 279 mm
  • No of Pages: 402
  • Spine Width: 21 mm
  • Weight: 925 gr
  • ISBN-10: 1361427361
  • Publisher Date: 27 Jan 2017
  • Binding: Paperback
  • Language: English
  • Series Title: English
  • Sub Title: Homoleptic D10-Metal Aryl/Alkylacetylides, Ruthenium N-Heterocycles and Picolinates
  • Width: 216 mm


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