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Supramolecular chemistry based on redox-active components and cucurbit[n]urils
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
2010 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis describes the host-guest chemistry between Cucurbit[7]uril (CB[7]) and CB[8] and a series of guests including bispyridinium cations, phenols and  napthalenes. These guests are bound to ruthenium polypyridine complexes or ruthenium based water oxidation catalysts (WOCs). The investigations are based upon utilizing the covalently linked photosensitizer and the electronic effects and chemical processes are investigated.

Place, publisher, year, edition, pages
Stockholm: KTH , 2010. , 59 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2010:38
Keyword [en]
Cucurbit[n]uril, redox-active, viologen, light-driven, water oxidation, molecular motor
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-24730ISBN: 978-91-7415-742-0 (print)OAI: oai:DiVA.org:kth-24730DiVA: diva2:353246
Public defence
2010-10-15, F3, Lindstedtsvägen 26, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Note
QC 20100927Available from: 2010-09-27 Created: 2010-09-24 Last updated: 2011-12-12Bibliographically approved
List of papers
1. The photoinduced long-lived charge-separated state of Ru(bPY)(3)-methylviologen with cucurbit 8 uril in aqueous solution
Open this publication in new window or tab >>The photoinduced long-lived charge-separated state of Ru(bPY)(3)-methylviologen with cucurbit 8 uril in aqueous solution
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2006 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, no 40, 4195-4197 p.Article in journal (Refereed) Published
Abstract [en]

A stable 1 : 1 inclusion complex of Ru(bpy)(3)-MV2+ with cucurbit[8]uril (CB[8]) is formed in aqueous solution; upon light irradiation, a long lived (tau similar to 2 mu s) charge-separated state Ru3+- MV+.-CB[8] is observed.

Keyword
artificial photosynthesis, cucurbituril homologs, molecular machine, electron-transfer, chemistry, complexes, driven
Identifiers
urn:nbn:se:kth:diva-16092 (URN)10.1039/b609015j (DOI)000241582100008 ()2-s2.0-33749682740 (Scopus ID)
Note

QC 20100525

Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2016-12-21Bibliographically approved
2. Host-guest chemistry and light driven molecular lock of Ru(bpy)(3)-viologen with cucurbit 7-8 urils
Open this publication in new window or tab >>Host-guest chemistry and light driven molecular lock of Ru(bpy)(3)-viologen with cucurbit 7-8 urils
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2007 (English)In: Journal of Physical Chemistry B, ISSN 1520-6106, E-ISSN 1520-5207, Vol. 111, no 47, 13357-13363 p.Article in journal (Refereed) Published
Abstract [en]

Host-guest chemistry and photoinduced electron-transfer processes have been studied in the systems containing Ru(bPy)(3) complex covalently linked to viologen as a guest molecule and cucurbit[n]urils (n = 7, 8) as host molecules in aqueous solution. The Ru(bpy)(3)-viologen complex,[Ru(2,2 '-bipyridine)(2)(4-(4-(1 '-methyl-4,4 '-bipyridinediium-1-yl)butyl)-4 '-methyl-2,2 '-bipyridine)]Cl-4(denoted as RU2+-MV2+, 1) was shown to form stable 1:1 inclusion complexes with cucurbit[7]uril (CB[7]) and cucurbit[8] uril (CB[8]). The binding modes are slightly different with CB[7] and CB[8]. CB[7] preferentially binds to part of the viologen residue in 1 together with the butyl chain, whereas CB[8] preferentially encloses the whole viologen residue. Photoinduced intramolecular electron transfer from the excited-state of the Ru moiety to MV2+ which is inserted into the cavity of the CBs occurred. Long-lived charge-separated states RU3+-MV+center dot, were generated with the lifetimes of 280 ns with CB[7] and 2060 ns with CB[8]. This shows that CBs can slow down the charge recombination within supramolecular systems, and the difference in lifetimes seems to be due to the difference in binding modes. In the presence of a sacrificial electron donor triethanolarnine, light-driven formation of a dimer of MV+center dot inside the CB[8] cavity was observed. This locked molecular dimer can be unlocked by molecular oxygen to give back the original form of the molecular dyad 1 with the MV2+ moiety inserted in the cavity of CB[8]. The processes could be repeated several times and showed nice reversibility.

Keyword
photoinduced electron-transfer, charge-transfer interactions, cation radicals, supramolecular assemblies, artificial photosynthesis, methyl viologen, tris-bipyridine, donor-acceptor, photosystem-ii, methylviologen
Identifiers
urn:nbn:se:kth:diva-17125 (URN)10.1021/jp074582j (DOI)000251140900002 ()2-s2.0-36949006481 (Scopus ID)
Note

QC 20100525

Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2016-12-19Bibliographically approved
3. Unusual partner radical trimer formation in a host complex of cucurbit 8 uril, ruthenium(II) tris-bipyridine linked phenol and methyl viologen
Open this publication in new window or tab >>Unusual partner radical trimer formation in a host complex of cucurbit 8 uril, ruthenium(II) tris-bipyridine linked phenol and methyl viologen
2010 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 46, no 3, 463-465 p.Article in journal (Refereed) Published
Abstract [en]

A stable 1 : 1 : 1 inclusion complex of Ru(bpy)(3)-phenol (1), MV2+ and cucurbit[8]uril (CB[8]) is formed in aqueous solution. In the presence of triethanolamine (TEOA), a light-induced formation of unusual partner radical trimer 1-(MV+center dot)(2)-CB[8] has been observed for the first time.

Keyword
ELECTRON-TRANSFER, CUCURBITURIL HOMOLOGS, CHARGE SEPARATION, MOLECULAR TRIAD, CATION RADICALS, METHYLVIOLOGEN, INCLUSION, CHEMISTRY, DRIVEN, FAMILY
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-19072 (URN)10.1039/b910575a (DOI)000272992700031 ()2-s2.0-75649117747 (Scopus ID)
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Note

QC 20100525

Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2016-12-16Bibliographically approved
4. Selective Positioning of CB 8 on Two Linked Viologens and Electrochemically Driven Movement of the Host Molecule
Open this publication in new window or tab >>Selective Positioning of CB 8 on Two Linked Viologens and Electrochemically Driven Movement of the Host Molecule
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2009 (English)In: European Journal of Organic Chemistry, ISSN 1434-193X, E-ISSN 1099-0690, no 8, 1163-1172 p.Article in journal (Refereed) Published
Abstract [en]

The binding interactions between cucurbit[8]uril (CB[8]) and a dicationic guest N,N-dimethyl-3,3'-dimethyl-4,4'-bipyridinium (DMV2+) have been investigated by various experimental techniques including NMR, ESI-MS, and UV/Vis and fluorescence spectroscopy. In a three-component system consisting of CB[81, N,N-dimethyl-4,4'-bipyridinium (MV2+) and DMV2+, CB[8] was found to exhibit a higher binding affinity to DMV2+ than to MV2+, When DMV2+ was connected to MV2+ by an alkyl chain, the first equiv. of CB[8] could be selectively positioned on the DMV2+ moiety, and then a second equiv. of CB[8] was positioned on the MV2+ moiety. Spectroelectrochemical studies showed that upon the reduction of this system at -0.6 V vs. AgCl, the CB[8] could move from the DMV2+ moiety to the MV+center dot radical, which formed a dimer inside the CB[8] cavity. Molecular oxygen quenched the dimer, and the CB[8] moved back to the DMV2+ moiety, indicating it molecular movement driven by electrochemistry. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Identifiers
urn:nbn:se:kth:diva-18254 (URN)10.1002/ejoc.200801012 (DOI)000264308100009 ()2-s2.0-62249117106 (Scopus ID)
Note

QC 20100525

Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2016-12-19Bibliographically approved
5. Light driven formation of a supramolecular system with three CB 8 s locked between redox-active Ru(bpy)(3) complexes
Open this publication in new window or tab >>Light driven formation of a supramolecular system with three CB 8 s locked between redox-active Ru(bpy)(3) complexes
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2009 (English)In: Organic and biomolecular chemistry, ISSN 1477-0520, E-ISSN 1477-0539, Vol. 7, no 17, 3605-3609 p.Article in journal (Refereed) Published
Abstract [en]

Three CB[8]s have been reversibly locked between two Ru(bpy)(3)-viologen complexes by light driven electron transfer reactions.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-18689 (URN)10.1039/b910112h (DOI)000268975300034 ()2-s2.0-70349266048 (Scopus ID)
Note
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2010-12-13Bibliographically approved
6. Selective binding of cucurbit 7 uril and beta-cyclodextrin with a redox-active molecular triad Ru(bpy)(3)-MV2+-naphthol
Open this publication in new window or tab >>Selective binding of cucurbit 7 uril and beta-cyclodextrin with a redox-active molecular triad Ru(bpy)(3)-MV2+-naphthol
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2007 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, no 45, 4734-4736 p.Article in journal (Refereed) Published
Abstract [en]

A 1:1:1 inclusion complex is formed by the binding interactions among beta-CD, CB[ 7] hosts, and Ru(bpy)(3)-terminated viologen naphthalene guest in aqueous solution, in which the positions of both CB[7] and beta-CD are closer to the Ru stopper than in the respective 1:1 inclusion complexes, forming a tightened nut on bolt'' structural mode.

Keyword
host-guest complexation, alpha-cyclodextrin, electron-transfer, pseudorotaxanes, driven, cucurbituril, derivatives, inclusion, chemistry, movement
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-17109 (URN)10.1039/b712980g (DOI)000250931100013 ()2-s2.0-36148935150 (Scopus ID)
Note

QC 20100525

Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2016-12-19Bibliographically approved
7. A host-induced intramolecular charge-transfer complex and light-driven radical cation formation of a molecular triad with cucurbit 8 uril
Open this publication in new window or tab >>A host-induced intramolecular charge-transfer complex and light-driven radical cation formation of a molecular triad with cucurbit 8 uril
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2008 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 73, no 10, 3775-3783 p.Article in journal (Refereed) Published
Abstract [en]

The host-guest chemistry of systems containing a molecular triad Ru(bpy)(3)-MV2+-naphthol complex (denoted as Ru2+-MV2+-Np, 1) and cucurbit[8]uril (CB[8]) is investigated by NMR, EST-MS, UV-vis, and electrochemistry. The Ru2+-MV2+-Np guest and CB [8] host can form a stable 1:1 inclusion complex, in which the naphthalene residue is back-folded and inserted together with the viologen residue into the cavity of CB[8]. The selective binding of Ru2+-MV2+-Np guest with beta-CD and CB[8] host is also investigated. We find that CB[8] binds the Ru2+-MV2+-Np guest stronger than beta-CD. Upon light irradiation, a MV+center dot radical cation stabilized in the cavity of CB[8] accompanied by the naphthalene residue has been observed. This novel system may open a new way for design and synthesis of photoactive molecular devices.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-17522 (URN)10.1021/jo800110b (DOI)000255698500015 ()2-s2.0-43449093454 (Scopus ID)
Note

QC 20100525

Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2016-12-19Bibliographically approved
8. Isolated Supramolecular [Ru(bpy)(3)]-Viologen-[Ru(bpy)(3)] Complexes with Trapped CB[7,8] and Photoinduced Electron-Transfer Study in Nonaqueous Solution
Open this publication in new window or tab >>Isolated Supramolecular [Ru(bpy)(3)]-Viologen-[Ru(bpy)(3)] Complexes with Trapped CB[7,8] and Photoinduced Electron-Transfer Study in Nonaqueous Solution
2011 (English)In: Chemistry - A European Journal, ISSN 0947-6539, Vol. 17, no 41, 11604-11612 p.Article in journal (Refereed) Published
Abstract [en]

The synthesis of two supramolecular diruthenium complexes, 1 subset of CB[7] and 1 subset of CB[8] (CB[n]=cucurbit[n]uril), which contain the respective host CB[7] and CB[8], were synthesized and isolated. In the case of host CB[8], the desired supramolecular complex was obtained by utilizing dihydroxynapthalene as a template during the synthesis. The (1)H NMR spectra, electrochemistry, and photochemistry of these supramolecular complexes were performed in nonaqueous solution. The results show that both CB[7,8] hosts mainly bind to the linker part in solution in acetonitrile. This binding also lowers the oxidation potential of the ruthenium metal center and hinders the quenching effect by the viologen moiety. It has also been shown that external methylviologen can be included into 1 subset of CB[8]. Analysis with NMR spectroscopy, electrochemistry, and photochemistry clearly shows a viologen radical dimer formation between the bound viologen and free methylviologen, thereby showing that the unique abilities of the CB[8] host can be utilized even in nonaqueous solution.

Keyword
cucurbit[8]uril, electron transfer, ruthenium, supramolecular chemistry, viologen
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-24820 (URN)10.1002/chem.201002618 (DOI)000297014400030 ()2-s2.0-80053195331 (Scopus ID)
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Note
QC 20100927. Uppdaterad från manuskript till artikel 20111212.Available from: 2010-09-27 Created: 2010-09-27 Last updated: 2011-12-12Bibliographically approved
9. An efficient water oxidation system based on supramolecular assembly of molecular catalyst and cucurbit[7]uril
Open this publication in new window or tab >>An efficient water oxidation system based on supramolecular assembly of molecular catalyst and cucurbit[7]uril
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-24821 (URN)
Note
QC 20100927Available from: 2010-09-27 Created: 2010-09-27 Last updated: 2010-09-27Bibliographically approved

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