Application of the 2-Pyridone Hydrogen-Bonding Motif in Supramolecular Catalysis and in Phenanthroline Based Ligands
(2005)- Abstract
- This thesis concentrates on the development, synthesis and evaluation of supramolecular systems, assembled from its components by means of hydrogen bonding, using the self-complementary 2-pyridone motif. The thesis is divided in two parts.
1) Supramolecular catalysis: Substrate selectivity is imposed on a derivative of Jacobsen's catalyst, an Mn(salen) complex with 2-quinolone hydrogen-bonding groups in the 5,5'-positions, by noncovalently attaching a receptor functionality, a Zn(tetraarylporphyrin) with appending 2-pyridone groups. The hydrogen-bonding functionalities are arranged in a way to favor the formation of a dynamic macrocyclic heterodimer. The resulting catalytic system shows substrate selectivity in the... (More) - This thesis concentrates on the development, synthesis and evaluation of supramolecular systems, assembled from its components by means of hydrogen bonding, using the self-complementary 2-pyridone motif. The thesis is divided in two parts.
1) Supramolecular catalysis: Substrate selectivity is imposed on a derivative of Jacobsen's catalyst, an Mn(salen) complex with 2-quinolone hydrogen-bonding groups in the 5,5'-positions, by noncovalently attaching a receptor functionality, a Zn(tetraarylporphyrin) with appending 2-pyridone groups. The hydrogen-bonding functionalities are arranged in a way to favor the formation of a dynamic macrocyclic heterodimer. The resulting catalytic system shows substrate selectivity in the Jacobsen-Katsuki (J-K) epoxidation, favoring pyridine appended styrene derivatives, capable of binding to the receptor, over phenyl appended ones. The substrate- and enantioselectivity of the catalyst as well as its reactivity and stability have been probed at various reaction conditions to obtain an understanding of the mechanisms underlying the substrate selectivity. In the interpretation of the results of the catalysis experiments, novel aspects on the mechanism of J-K epoxidation have emerged. Suggestions on how to improve the substrate selectivity in future generations of the present supramolecular catalytic system have also been derived from these results.
2) Phenanthroline based ligands: Solid state structures of a 2-pyridone fused phenanthroline based (phenamide) ligand and its Cu(I) complex were analyzed. Both revealed unexpected hydrogen bonding behavior of the 2-pyridone moiety. The free ligand crystallized in the highly unusual packing mode P-1 Z = 7, Z' = 3.5. The Cu(I) complex is a potential building block for chiral linear hydrogen-bonded coordination polymers, but the Cu(I) complex of the first generation of phenamide ligand did not produce the anticipated polymer structure in the solid state. The observed structure was a result of competition between hydrogen-bonding and pi-stacking. (Less) - Abstract (Swedish)
- Popular Abstract in Swedish
Det största bidraget till komplexitet i kemiska system kommer inte från de kemiska komponenternas molekulära struktur, utan deras växelverkan med varandra. Vi har mycket större kännedom om molekylär struktur i biologiska celler och organismer än om detaljerna i deras växelverkan. Ändå är det precis växelverkan mellan molekyler som utgör alla biologiska processer i grunden. Vikten av at studera och lära känna grundmekanismerna bakom molekylär växelverkan har så småningom blivit mer och mer uppenbar. Den kunskapen kan både användas för att uppnå bättre förståelse om biologiska processer och funktion och till systematisk tillämpning av olika typer av växelverkan för design och framställning av... (More) - Popular Abstract in Swedish
Det största bidraget till komplexitet i kemiska system kommer inte från de kemiska komponenternas molekulära struktur, utan deras växelverkan med varandra. Vi har mycket större kännedom om molekylär struktur i biologiska celler och organismer än om detaljerna i deras växelverkan. Ändå är det precis växelverkan mellan molekyler som utgör alla biologiska processer i grunden. Vikten av at studera och lära känna grundmekanismerna bakom molekylär växelverkan har så småningom blivit mer och mer uppenbar. Den kunskapen kan både användas för att uppnå bättre förståelse om biologiska processer och funktion och till systematisk tillämpning av olika typer av växelverkan för design och framställning av konstgjorda funktionella kemiska system, uppbyggda av flera molekylära komponenter.
Den senare tillämpningen utgör forskningsfältet supramolekylär kemi, där man utvecklar och använder strukturella motiv för intermolekylär växelverkan för att framställa nya konstgjorda material med hittills okända egenskaper. Man försöker också härma egenskaper som är kända från biokemiska system. Konstgjorda receptorer, sensorer för medicinskt viktiga biologiska kemikalier och miljögifter, katalysatorer med enzymliknande egenskaper och nanotekniska material är bland det som har utvecklats med systematisk användning av intermolekylär växelverkan.
I forskningen som presenteras i denna avhandling har man fokuserad på s.k. vätebindningar som motiv för intermolekylär växelverkan. Man har tagit ett vätebindningsmotiv, 2-pyridon dimer, och använt det som ett molekylärt klister. Med hjälp av det motivet har man konstruerat en nanokavitet runt ett katalytiskt centrum genom att klistra ihop en katalysatorenhet med en receptorenhet, och därmed infört selektivitet hos katalysatorn, då den heller reagerar med substrat som binder till receptoren än de som inte binder.
I ett annat projekt i avhandlingen har man försökt konstruera polymer material som består av en ny metall ligand som även innehåller 2-pyridon vätebindningsmotivet, så att enskilda metallkomplex av liganden skall kunna klistras ihop med hjälp av vätebindningar och därigenom bilda polymerer. Dessa polymerer skulle kunna ha tillämpningar inom nanoteknologi. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/545270
- author
- Jonsson, Stefan LU
- supervisor
- opponent
-
- Professor Sanders, Jeremy K. M., University of Cambridge
- organization
- publishing date
- 2005
- type
- Thesis
- publication status
- published
- subject
- keywords
- Organic chemistry, X-ray crystallography, Phenanthroline, Supramolecular Catalysis, Jacobsen-Katsuki Epoxidation, Mn(salen), Hydrogen-bonding, Supramolecular Chemistry, 2-Pyridone, Organisk kemi
- pages
- 109 pages
- publisher
- Organic Chemistry, Lund University
- defense location
- Sal F, Kemicentrum, Getingevägen 60, Lund
- defense date
- 2005-09-22 10:30:00
- ISBN
- 91-628-6603-6
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Organic chemistry (S/LTH) (011001240)
- id
- d02c7889-4f89-4d12-bfce-c1f3ec30a519 (old id 545270)
- date added to LUP
- 2016-04-04 10:04:33
- date last changed
- 2018-11-21 20:56:34
@phdthesis{d02c7889-4f89-4d12-bfce-c1f3ec30a519,
abstract = {{This thesis concentrates on the development, synthesis and evaluation of supramolecular systems, assembled from its components by means of hydrogen bonding, using the self-complementary 2-pyridone motif. The thesis is divided in two parts.<br/><br>
<br/><br>
1) Supramolecular catalysis: Substrate selectivity is imposed on a derivative of Jacobsen's catalyst, an Mn(salen) complex with 2-quinolone hydrogen-bonding groups in the 5,5'-positions, by noncovalently attaching a receptor functionality, a Zn(tetraarylporphyrin) with appending 2-pyridone groups. The hydrogen-bonding functionalities are arranged in a way to favor the formation of a dynamic macrocyclic heterodimer. The resulting catalytic system shows substrate selectivity in the Jacobsen-Katsuki (J-K) epoxidation, favoring pyridine appended styrene derivatives, capable of binding to the receptor, over phenyl appended ones. The substrate- and enantioselectivity of the catalyst as well as its reactivity and stability have been probed at various reaction conditions to obtain an understanding of the mechanisms underlying the substrate selectivity. In the interpretation of the results of the catalysis experiments, novel aspects on the mechanism of J-K epoxidation have emerged. Suggestions on how to improve the substrate selectivity in future generations of the present supramolecular catalytic system have also been derived from these results.<br/><br>
<br/><br>
2) Phenanthroline based ligands: Solid state structures of a 2-pyridone fused phenanthroline based (phenamide) ligand and its Cu(I) complex were analyzed. Both revealed unexpected hydrogen bonding behavior of the 2-pyridone moiety. The free ligand crystallized in the highly unusual packing mode P-1 Z = 7, Z' = 3.5. The Cu(I) complex is a potential building block for chiral linear hydrogen-bonded coordination polymers, but the Cu(I) complex of the first generation of phenamide ligand did not produce the anticipated polymer structure in the solid state. The observed structure was a result of competition between hydrogen-bonding and pi-stacking.}},
author = {{Jonsson, Stefan}},
isbn = {{91-628-6603-6}},
keywords = {{Organic chemistry; X-ray crystallography; Phenanthroline; Supramolecular Catalysis; Jacobsen-Katsuki Epoxidation; Mn(salen); Hydrogen-bonding; Supramolecular Chemistry; 2-Pyridone; Organisk kemi}},
language = {{eng}},
publisher = {{Organic Chemistry, Lund University}},
school = {{Lund University}},
title = {{Application of the 2-Pyridone Hydrogen-Bonding Motif in Supramolecular Catalysis and in Phenanthroline Based Ligands}},
year = {{2005}},
}