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Synthesis of a novel bis-Mg-porphyrin tweezer
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Organic Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Organic Chemistry.ORCID iD: 0000-0002-9092-261X
(English)Manuscript (preprint) (Other academic)
Abstract [en]

We have synthesised a novel semi-rigid bis-(magnesium-porphyrin) tweezer with a glycoluril backbone. meso-Tetrakis(pentafluorophenyl)porphyrin constitutes the two porphyrin units, each holding a magnesium(II) ion, and being connected to the glycoluril backbone via two -positions. This connection prevents any porphyrin rotation, leaving changes in gap size as sole conformational variation. Magnesium(II) tetrakis(pentafluorophenyl)porphyrin has in previous studies shown to bind well to both nitrogen-containing and oxygen-containing functional groups. The tweezer has the potential to retain this binding ability, which would be useful in the stereochemical characterization of small flexible molecules with multiple stereocentra and a wide variety of functional groups.

Keywords [en]
magnesium-porphyrin tweezer synthesis
National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-382217OAI: oai:DiVA.org:uu-382217DiVA, id: diva2:1306273
Funder
Swedish Research Council, 621-2012-3379Carl Tryggers foundation , CTS 16:156Available from: 2019-04-23 Created: 2019-04-23 Last updated: 2019-04-23
In thesis
1. Host-Guest Interactions for Structural Analysis of Organic Molecules: Development of new Tools for Stereochemical Characterization
Open this publication in new window or tab >>Host-Guest Interactions for Structural Analysis of Organic Molecules: Development of new Tools for Stereochemical Characterization
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The focus of this thesis is on the development of molecular tweezers as host-guest systems for stereochemical characterization of small organic molecules.

There are two central problems to stereochemical characterization of small molecules. The first is that there are few methods for the determination of absolute stereochemistry and the complexity of the task increases with the number of chiral centres in the molecule. The second is the flexibility of small molecules. The data received from NMR spectroscopy, the standard method for structural characterization is an average of all conformers present in solution, making exact determination of the structure challenging if stereocenters are involved.

This research group has previously developed two bis-porphyrin molecular tweezers that can be used as hosts for relative stereochemical determination by NMR (NAMFIS) by limiting the flexibility of the guest molecules and for absolute stereochemical determination Exciton-Coupled Circular Dichroism (ECCD) by providing suitable chromophores. However, the use of these tweezers was limited to diamine molecules.

To extend the application of both tweezer host systems, a range of metalloporphyrins have been investigated both computationally and experimentally to identify candidates binding strongly to oxygen containing functional groups (Paper I). One of the porphyrins identified has been used to synthesise a new system with the potential to be used for relative stereochemical determination by NMR (NAMFIS) of molecules with a wide variety of functional groups (Paper IV).

To further develop the systems, the photo-isomerization properties of the stiff stilbene linker of one of the tweezers has been investigated. Macrocyclic diether model compounds, incorporating the stiff stilbene linker have been used to show that the photo-isomerizability strongly is affected by molecular strain (Paper II). The results suggest that if paired with a suitable porphyrin (with no UV/Vis absorption overlap) a photo-switchable tweezer might be constructed.

To map the guest range of the stiff stilbene linked tweezer it was found that this tweezer gives strong to moderate signals for monoamines with a rigid structure (Paper III). As ditopic binding is usually a requirement for an ECCD signal when using bis-porphyrin molecular tweezers, this is a discovery that should be of general interest.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2019. p. 63
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1810
Keywords
metalloporphyrins, host-guest systems, bis-porphyrin tweezers, stiff stilbene macrocycles, organic synthesis, porphyrin binding studies, NMR, ECCD
National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-382219 (URN)978-91-513-0660-5 (ISBN)
Public defence
2019-06-14, Room A1:107, BMC, Husargatan 3, Uppsala, 09:15 (English)
Opponent
Supervisors
Available from: 2019-05-22 Created: 2019-04-23 Last updated: 2019-06-18

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Olsson, Sandra K.Gogoll, Adolf

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