Study on Synthesis Structures and Properties of Bridged Diruthenium and Dicopper Complexes

  • 許 樂群

Student thesis: Doctoral Thesis

Abstract

Supramolecular cages can be synthesized via symmetry-interaction directional-bonding weak-link and dynamic-self-assembly approaches Both experimental and theoretical study of a simple dynamic system formed between dicopper complex [Cu2(μ-dppm)2(μ-OAc)]+ and various sigma donors (L; L = py MeCN THF acetone MeOH) in CH2Cl2 and study of that between dicopper complexes [Cu2(μ-dppm)2(μ-O2CR)]+ and neutral dipyridyl compound (NN NN = 4 4’-bipyridine (bpy) 1 2-bis(4-pyridyl)ethane (bpa) and trans-1 2-bis(4-pyridyl)ethylene (bpe) and 4 4’-trimethylenedipyridine (tmp)) led us to study dynamic systems between tetracopper complex [{Cu2(μ-dppm)2}2(μ-1 3-C6H4(CO2)2)]2+ andNN (NN = bpa tmp bpy) unexpectedly finding that the flexibility of NN can determine the outcome of the dynamic reactions The flexible NN can convert the tetracopper complex into supramolecular cages but the rigid NN can convert the complex into a coordination polymer The dynamic system between tetracopper complex [{Cu2(μ-dppm)2}2(μ-(1 4-C6H4(CO2)2)]2+ andNN (NN = bpa bpy) can produce a rectangular cationic cage [{(Cu2(μ-dppm)2)2(μ-1 4-C6H4(CO2)2)}2(μ-bpa)2]4+ with an anion (BF4-) inside and three other anions outside The study finds that the weak electrostatic interactions between the cationic cage and the anion are important in stabilizing the dynamically self-assembled cages Diruthenium carbonyl complexes containing two nitrito and nitrato ligands [Ru2(μ-CO)2(κ2-(O O’)-NO2)2(μ-dppm)2] (2-6) and [Ru2(μ-CO)2(κ2-(O O’)-NO3)2(μ-dppm)2] (2-10) were prepared Conversion reactions of compound 2-6 into [Ru2(μ-dppm)2(μ-CO)2(MeCN)4](BF4)2 [Ru2(μ-dppm)2(CO)2(tBuNC)4](PF6)2 [Ru2(μ-dppm)2(CO)2(μ-NO)(μ-Cl)Cl2] (2-8) and [Ru2(μ-dppm)2(CO)2(μ-H)(μ-Cl)Cl2] (2-9) were also studied Crystal structures of compounds 2-6 2-8 2-9 and 2-10 were determined by X-ray crystallography
Date of Award2017 Apr 24
Original languageEnglish
SupervisorTian-Shung Wu (Supervisor)

Cite this

Study on Synthesis Structures and Properties of Bridged Diruthenium and Dicopper Complexes
樂群, 許. (Author). 2017 Apr 24

Student thesis: Doctoral Thesis