Supramolecular chemistry is a multidisciplinary field which impinges on other disciplines, focusing
on the systems made up of a discrete number of assembled molecular subunits. The forces
responsible for the spatial organization are intermolecular reversible interactions.
The supramolecular architectures I was interested in are Rotaxanes, mechanically-interlocked
architectures consisting of a "dumbbell shaped molecule", threaded through a "macrocycle" where
the stoppers at the end of the dumbbell prevent disassociation of components and catenanes, two or
more interlocked macrocycles which cannot be separated without breaking the covalent bonds.
The aim is to introduce one or more paramagnetic units to use the ESR spectroscopy to investigate
complexation properties of these systems cause this technique works in the same time scale of
supramolecular assemblies.
Chapter 1 underlines the main concepts upon which supramolecular chemistry is based, clarifying
the nature of supramolecular interactions and the principles of host-guest chemistry.
In chapter 2 it is pointed out the use of ESR spectroscopy to investigate the properties of organic
non-covalent assemblies in liquid solution by spin labels and spin probes. The chapter 3 deals with
the synthesis of a new class of p-electron-deficient tetracationic cyclophane ring, carrying one or
two paramagnetic side-arms based on 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) moiety.
In the chapter 4, the Huisgen 1,3-dipolar cycloaddition is exploited to synthesize rotaxanes having
paramagnetic cyclodextrins as wheels.
In the chapter 5, the catalysis of Huisgen’s cycloaddition by CB[6] is exploited to synthesize
paramagnetic CB[6]-based [3]-rotaxanes.
In the chapter 6 I reported the first preliminary studies of Actinoid series as a new class of
templates in catenanes’ synthesis. Being f-block elements, so having the property of expanding the
valence state, they constitute promising candidates as chemical templates offering the possibility to
create a complex with coordination number beyond 6.
| Identifer | oai:union.ndltd.org:unibo.it/oai:amsdottorato.cib.unibo.it:3778 |
| Date | 12 April 2011 |
| Creators | Casati, Costanza <1984> |
| Contributors | Lucarini, Marco |
| Publisher | Alma Mater Studiorum - Università di Bologna |
| Source Sets | Università di Bologna |
| Language | Italian |
| Detected Language | English |
| Type | Doctoral Thesis, PeerReviewed |
| Format | application/pdf |
| Rights | info:eu-repo/semantics/openAccess |
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