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Development of Novel Hydroporphyrins for Light Harvesting and Sensitising NIR Lanthanide Luminescence
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström.
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Chlorins, as the core structures of chlorophylls, have been extensively studied for harvesting solar energy, fluorescent imaging and photodynamic therapy against cancer. This thesis is concerned with design and synthesis of novel chlorins as antennae for harvesting light and sensitising near infrared lanthanide luminescence.

In the first part, a series of chlorin monomers, dimers and polymers were synthesised and their photophysical properties were characterised. The chlorin monomers were substituted with five-membered heterocycles, such as thiophenes and furans. These heterocycles function as auxochromes analogous to the natural ones in chlorophylls, and extend chlorin absorption and emission strongly to the red (up to λem = 680 nm). A borylation method was developed to prepare borylated chlorins, which gave access to directly linked chlorin dimers through Suzuki coupling reaction. Different regioisomers of chlorin dimer were prepared, including β-meso homodimers, meso-meso homodimers and heterodimers. The dimerisation resulted in red-shifted absorption and emission. Chlorin polymerisations were performed both electrochemically and chemically. Bis-thienylchlorins yielded chlorin films and an organic solvent soluble copolymer with hexylthiophene, respectively. These polymers from both polymerisations have red absorptions beyond 700 nm, and might be used as light-harvesting antennae.

In the second part, chlorins were used as chromophores to sensitise near infrared lanthanide luminescence. Two types of chlorin-lanthanide dyads were prepared through lanthanide coordination with cyclen derivatives and dipicolinic acids (DPA). The cyclen-based dyads were poorly soluble in water, thus their near infrared emissions were not observed. The other type of complexes was fully soluble in H2O and THF. Both Nd and Yb emission were recorded even upon excitation into the Q bands of chlorins. In the dyads with free base chlorins, the singlet state of chlorins might be involved in the sensitisation of lanthanide luminescence. These DPA-based dyads presented two-color emission based on one chlorin and two-color excitation based on one lanthanide ion. These dyads would enable in theory 4-color imaging.

In the last part, a microwave-assisted two-step synthesis was described to prepare dipyrromethanes, which are the key intermediates in the chlorin synthesis. This mild method took advantage of the nucleophilicity of pyrrole and the electrophilicity of N,N-dimethylaminomethyl pyrroles. The usually used acid catalysis is detrimental to many functionalities, thus our methods enable the synthesis of dipyrromethanes with acid sensitive groups or a formyl group.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2017. , p. 78
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1509
Keywords [en]
chlorin, hydroporphyrin, chlorophyll analogues, light harvesting, lanthanide luminescence
National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-319909ISBN: 978-91-554-9898-6 (print)OAI: oai:DiVA.org:uu-319909DiVA, id: diva2:1087987
Public defence
2017-06-02, 2001, Ångstroöm laboratory, Lägerhyddsvägen 1, Uppsala, 13:15 (English)
Opponent
Supervisors
Available from: 2017-05-12 Created: 2017-04-10 Last updated: 2017-05-29
List of papers
1. Furan- and Thiophene-Based Auxochromes Red-shift Chlorin Absorptions and Enable Oxidative Chlorin Polymerizations
Open this publication in new window or tab >>Furan- and Thiophene-Based Auxochromes Red-shift Chlorin Absorptions and Enable Oxidative Chlorin Polymerizations
Show others...
2017 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 23, no 17, p. 4089-4095Article in journal (Refereed) Published
Abstract [en]

The de novo syntheses of chemically stable chlorins with five-membered heterocyclic (furane, thiophene, formylfurane and formylthiophene) substituents in selected meso- and beta-positions are reported. Heterocycle incorporation in the 3- and 13-positions shifted the chlorin absorption and emission to the red (up to lambdaem =680 nm), thus these readily incorporated substituents function analogously to auxochromes present in chlorophylls, for example, formyl and vinyl groups. Photophysical, theoretical and X-ray crystallographic experiments revealed small but significant differences between the behavior of the furan- and the thiophene-based auxochromes. Four regioisomeric bis-thienylchlorins (3,10; 3,13, 3,15 and 10,15) were oxidatively electropolymerized; the chlorin monomer geometry had a profound impact on the polymerization efficiency and the electrochemical properties of the resulting material. Chemical co-polymerization of 3,13-bis-thienylchlorin with 3-hexylthiophene yielded an organic-soluble red-emitting polymer.

Keywords
chlorins, electrochemistry, photophysics, polymerization, porphyrinoids
National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-317978 (URN)10.1002/chem.201604655 (DOI)000399312700011 ()27859811 (PubMedID)
Funder
Stiftelsen Olle Engkvist ByggmästareSwedish Research Council, 2013-4655Swedish Research Council, 2013-4763
Available from: 2017-03-22 Created: 2017-03-22 Last updated: 2017-12-28Bibliographically approved
2. Directly linked hydroporphyrin dimers
Open this publication in new window or tab >>Directly linked hydroporphyrin dimers
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2016 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 52, no 58, p. 9056-9058Article in journal (Refereed) Published
Abstract [en]

Directly linked hydroporphyrin (chlorin) dimers were accessed regioselectively from bromochlorins. Versatile 15-borylated chlorins were prepared in excellent yield via Miyaura borylation. Suzuki coupling yielded meso-beta-linked homo- and heterodimers, and meso-blinked dimers. The photophysical and electrochemical properties of the dimers are reported.

National Category
Other Chemistry Topics
Identifiers
urn:nbn:se:uu:diva-300581 (URN)10.1039/c6cc00516k (DOI)000379431000018 ()26859412 (PubMedID)
Funder
Swedish Research Council, 2013-4655Stiftelsen Olle Engkvist Byggmästare
Available from: 2016-08-09 Created: 2016-08-09 Last updated: 2017-11-28Bibliographically approved
3. Synthesis and characterisation of lanthanide-hydroporphyrin dyads
Open this publication in new window or tab >>Synthesis and characterisation of lanthanide-hydroporphyrin dyads
2015 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 44, p. 2541-2553Article in journal (Refereed) Published
Abstract [en]

Fluorescence spectroscopy is in many ways the ideal tool for the interrogation of complex biological systems, as it is non-invasive, sensitive, and offers high spatiotemporal resolution. For biomedical imaging luminescent probes absorbing and emitting in the red-to-near infrared (NIR) region are best suited to maximise tissue penetration and minimise damage to cellular components. NIR-emitting lanthanides (Ln) sensitised with red-absorbing antennae are promising candidates for these applications, assuming the challenges of poor photophysical properties and tedious syntheses of the complexes are overcome. Chlorins are porphyrin-type tetrapyrroles with intense red absorption. Recently chlorins have been shown to sensitise Yb and Nd emission when incorporated into Ln-complexes. Here we expand on our previous work, and explore the effect of chlorin structure, metallation state, chlorin-Ln-complex linker length and mode of attachment on the properties of chlorin-Ln complexes. As chlorin absorption bands are approximately 20 nm fwhm and readily tunable, a deeper understanding of structure-property relationships would enable the use of chlorin-Ln complexes in multicolour imaging using antenna-specific excitation. A detailed description of antenna and complex syntheses and photophysical characterisation is given. A number of challenges were identified, which will have to be addressed in future studies to enable multicolour imaging using the NIR-emitting lanthanides.

National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-317982 (URN)
Funder
Swedish Research Council, 2013-4655Stiftelsen Olle Engkvist Byggmästare
Available from: 2017-03-22 Created: 2017-03-22 Last updated: 2017-11-29
4. Excitation- and emission wavelength-based multiplex imaging using red-absorbing near infrared-emitting lanthanide complexes
Open this publication in new window or tab >>Excitation- and emission wavelength-based multiplex imaging using red-absorbing near infrared-emitting lanthanide complexes
(English)Manuscript (preprint) (Other academic)
Abstract [en]

: Multiplex luminescence imaging in the red and near infrared (NIR) should be an enabling tool for the real-time investigation of complex biological systems. Current probes have numerous limitations including low photostability, short luminescent lifetime, overlapping absorption and emission bands, and small Stokes shift, the combination of which limits multiplexing in this region to two colors. Here we report emitters based on near infrared (NIR) emitting luminescent lanthanides (Ln) sensitized by hydroporphyin antennae. The narrow and intense absorption bands of hydroporphyrins are in the red, and their porisiotns are readily tunable. These dyads enable both emission- and excitation-based multiplexing; the former by combining either the same antenna with different Ln’s, the latter by attaching chlorin antennae with non-overlapping absorptions to the same Ln-complex. Up to 4 different species could be discerned without tedious data manipulation.

National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-319907 (URN)
Available from: 2017-04-10 Created: 2017-04-10 Last updated: 2017-04-10
5. Mild Microwave-Assisted Synthesis of Dipyrromethanes and Their Analogues
Open this publication in new window or tab >>Mild Microwave-Assisted Synthesis of Dipyrromethanes and Their Analogues
2014 (English)In: Synlett: Accounts and Rapid Communications in Synthetic Organic Chemistry, ISSN 0936-5214, E-ISSN 1437-2096, Vol. 26, p. 484-488Article in journal (Refereed) Published
Abstract [en]

The Mannich reaction between pyrroles or indoles and Eschenmoser’s salt (dimethylmethylideneammonium iodide) forms N,N-dimethylamino-methylated derivatives in good to excellent yields. The reaction is highly regioselective, and for pyrroles both 2- and 3-sub- stituted derivatives could be obtained. The N,N-dimethylaminometh- ylpyrroles and indoles underwent substitution with pyrrole under mi- crowave irradiation, affording the appropriate dipyrromethanes, N- confused, and indolo-dipyrromethanes in moderate to excellent overall yield. 

Keywords
pyrroles, indoles, heterocycles, microwave synthesis, dipyrromethanes
National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-317983 (URN)10.1055/s-0034-1378925 (DOI)
Funder
Swedish Research Council, 2013-4655
Available from: 2017-03-22 Created: 2017-03-22 Last updated: 2017-11-29

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