Multivalent Supramolecular Systems
type: CreativeWork
description: Nature uses multivalency as one of the most important governing principles to control selective molecular recognition and assembly. By combining a large number of weak interactions, it is possible to obtain high affinity, selective and reversible non-covalent binding processes. Multivalency has also become an important tool in the design of synthetic molecular systems. The result of multiple binding events is not just a simple sum of individual contributions due to cooperative interactions between binding sites. The main part of this thesis deals with the study of chelate cooperativity in multivalent supramolecular systems. Firstly, a well-known H-bonded rosette system was revisited and the effective molarity was determined experimentally by 1H NMR titrations to be around 2 M, which is a high chelate cooperativity compared to other supramolecular systems. Moreover, the concept of peripheral crowding in solution was revisited, since rosettes based on less bulky pyrimidines showed higher stabilities and effective molarities than the rosettes based on bulky pyrimidines. The following two chapters deal with efforts towards a supramolecular system inside a porphyrin nanoring. The porphyrin nanoring shows the highest value of effective molarity reported in the literature and is, therefore, a great system to study the cooperative behaviour when a covalent ligand is replaced with a supramolecular system. The first studied system was based on small molecules containing simple hydrogen-bond acceptors and donors. Unfortunately, solubility issues led to the termination of the project. The second system used the hydrogen-bonded rosette motif. A number of different pyridine-pyrimidine and pyridinebarbiturate ligands were synthesised and their assembly inside the porphyrin nanoring was studied in detail by UV-vis-NIR experiments. The effective molarities for the sequential binding of the rosette systems to 6-ring were determined to range from 0.23 to 3.7 M, which is significantly …
abstract: Nature uses multivalency as one of the most important governing principles to control selective molecular recognition and assembly. By combining a large number of weak interactions, it is possible to obtain high affinity, selective and reversible non-covalent binding processes. Multivalency has also become an important tool in the design of synthetic molecular systems. The result of multiple binding events is not just a simple sum of individual contributions due to cooperative interactions between binding sites. The main part of this thesis deals with the study of chelate cooperativity in multivalent supramolecular systems. Firstly, a well-known H-bonded rosette system was revisited and the effective molarity was determined experimentally by 1H NMR titrations to be around 2 M, which is a high chelate cooperativity compared to other supramolecular systems. Moreover, the concept of peripheral crowding in solution was revisited, since rosettes based on less bulky pyrimidines showed higher stabilities and effective molarities than the rosettes based on bulky pyrimidines. The following two chapters deal with efforts towards a supramolecular system inside a porphyrin nanoring. The porphyrin nanoring shows the highest value of effective molarity reported in the literature and is, therefore, a great system to study the cooperative behaviour when a covalent ligand is replaced with a supramolecular system. The first studied system was based on small molecules containing simple hydrogen-bond acceptors and donors. Unfortunately, solubility issues led to the termination of the project. The second system used the hydrogen-bonded rosette motif. A number of different pyridine-pyrimidine and pyridinebarbiturate ligands were synthesised and their assembly inside the porphyrin nanoring was studied in detail by UV-vis-NIR experiments. The effective molarities for the sequential binding of the rosette systems to 6-ring were determined to range from 0.23 to 3.7 M, which is significantly …
author: Motloch, Petr
language: eng
keywords: multivalency, cooperativity, supramolecular chemistry, effective molarity
license: https://apollo8-f-pro.lib.cam.ac.uk/bitstreams/06ecbc29-b971-4a46-ab26-f020d07f958f/download
license: https://www.rioxx.net/licenses/all-rights-reserved/
date published: 2019-09-30
date modified: 2026-07-22T22:24:01Z
provider: Cambridge University
publisher: Networked Digital Library of Theses and Dissertations
type: WebPage
source organization: University of Cambridge

PropertyValue
property ID: DOI
value: 10.17863/CAM.57312