Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
New Cu-I cluster compounds with luminescent properties
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
2011 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The aim of this thesis has been to investigate how the synthesis route, choice of solvent and counter-ions effects the crystallization of Cu(I)I systems, and to investigate the correlation between the structure and luminescence properties of the systems.

In order to do so a series of compounds based on an anion containing Cu(I)I, stabilized by organic cations have been produced. The crystal structures have been determined by single crystal X-ray crystallography. The luminescence properties have been quantified by laser confocal microscopy or by fluorescence spectrophotometry. We have also performed quantum mechanical calculations (Time Dependent Density Functional Theory (TDDFT)) to increase the understanding of the luminescence properties of the title system.

Incorporation of tetraalkylammonium with different chain-size showed that the size of the counter-ion matters, where small counter-ion give rise to formation of infinite chains and large and bulky counter-ion tends to form discrete anion. However, the effect of incorporation of different phosphonium based cations was not as consistent, hence the conclusion must be that the size of the cation matters only sometimes. Two different synthesis routes have been employed during this study, the solvolysis method and the hydrothermal method. The latter method showed to be very efficient for this system. Hydrothermal conditions do, however, tend to give rise to the formation of the thermodynamically most stable product and the combination of the two approaches is beneficial for a wider scan of the phase space.

Place, publisher, year, edition, pages
Stockholm: Department of Materials and Environmental Chemistry (MMK), Stockholm University , 2011. , 51 p.
Keyword [en]
Copper (I) iodide, structure determination, luminescence, TDDFT
National Category
Materials Chemistry
Research subject
Materials Chemistry
Identifiers
URN: urn:nbn:se:su:diva-54910ISBN: 978-91-7447-240-0 (print)OAI: oai:DiVA.org:su-54910DiVA: diva2:399887
Public defence
2011-04-13, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 09:00 (English)
Opponent
Supervisors
Note
At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: In press. Paper 6: Submitted. Paper 7: Submitted. Paper 8: Submitted. Paper 9: Manuscript. Available from: 2011-03-22 Created: 2011-02-21 Last updated: 2011-04-05Bibliographically approved
List of papers
1. Bis(isopropyltriphenylphosphonium) di-μ-iodido-bis[iodidocopper(I)]
Open this publication in new window or tab >>Bis(isopropyltriphenylphosphonium) di-μ-iodido-bis[iodidocopper(I)]
2010 (English)In: Acta Crystallographica Section E: Structure Reports Online, ISSN 1600-5368, E-ISSN 1600-5368, ISSN 1600-5368, no E66, m432-m433 p.Article in journal (Refereed) Published
Abstract [en]

The title compound, (C21H22P)2[Cu2I4], prepared from reaction between copper powder, iodine and isopropyl triphenylphosphonium iodide in hydroxyacetone (acetol), shows an already known Cu2I42- anion with a planar conformation [Cu-I range = 2.5108 (3)-2.5844 (3) Å and I-Cu-I range = 110.821 (10)-125.401 (10)°].

Keyword
copper iodide
National Category
Chemical Sciences
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-42777 (URN)10.1107/S1600536810010196 (DOI)000276190700069 ()
Available from: 2010-09-14 Created: 2010-09-14 Last updated: 2017-12-12Bibliographically approved
2. Bis(tetrapropylammonium) di-μ3-iodido-di-μ2-iodido-diiodidodipyridinetetracopper(I)
Open this publication in new window or tab >>Bis(tetrapropylammonium) di-μ3-iodido-di-μ2-iodido-diiodidodipyridinetetracopper(I)
2010 (English)In: Acta Crystallographica Section E: Structure Reports Online, ISSN 1600-5368, E-ISSN 1600-5368, Vol. 66, no E66, m431- p.Article in journal (Refereed) Published
Abstract [en]

The title compound, (C12H28N)2[Cu3.194I6(C5H5N)2] was prepared from reaction of copper powder, copper(I) oxide, hydroiodic acid, tetrapropylammonium iodide and pyridine under hydrothermal conditions. In the centrosymmetric Cu4I62- anion, one Cu site is in a trigonal-planar coordination while the second Cu site, which is only partially occupied [site occupancy of 0.5968 (16)], is surroundedby three iodine atoms and one pyridine molecule in a distorted tetrahedral coordination

Keyword
copper iodide
National Category
Chemical Sciences
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-42778 (URN)10.1107/S1600536810010202 (DOI)000276190700068 ()
Available from: 2010-09-14 Created: 2010-09-14 Last updated: 2017-12-12Bibliographically approved
3. Bis(μ3-iodo)-pentakis(μ2-iodo)-penta-copper(I) e: A fully ordered, isolated [Cu5I7]2 cluster
Open this publication in new window or tab >>Bis(μ3-iodo)-pentakis(μ2-iodo)-penta-copper(I) e: A fully ordered, isolated [Cu5I7]2 cluster
2011 (English)In: Solid State Sciences, ISSN 1293-2558, E-ISSN 1873-3085, Vol. 13, no 4, 768-772 p.Article in journal (Refereed) Published
Abstract [en]

Two new compounds, [(C4H9)4P]2[Cu5I7] and [(C4H9)4P]2[Cu5I7]·CH3COCH2OH were synthesized by solvolysis and their crystal structures were solved. The first compound is disordered, but the solvate represents the first example of a fully ordered [Cu5I7]2− cluster. It displays a molecular symmetry very close to C2. Both compounds crystallize in space group P21/c.

Keyword
copper (I) iodide cluster structure
National Category
Chemical Sciences
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-42782 (URN)10.1016/j.solidstatesciences.2010.03.019 (DOI)000289965900014 ()
Available from: 2010-09-14 Created: 2010-09-14 Last updated: 2017-12-12Bibliographically approved
4. Poly[dimethyldiphenylphosphonium [di-μ4-iodido-tetra-μ3-iodido-pentacopper(I)]]
Open this publication in new window or tab >>Poly[dimethyldiphenylphosphonium [di-μ4-iodido-tetra-μ3-iodido-pentacopper(I)]]
2010 (English)In: Acta Crystallographica Section C: Crystal Structure Communications, ISSN 0108-2701, E-ISSN 1600-5759, no C66, m227-m230 p.Article in journal (Refereed) Published
Abstract [en]

The title compound, {(C14H16P)[Cu5I6]}n, prepared from the reaction between copper powder, iodine and dimethyldiphenylphosphonium iodide in hydroxyacetone, features an anion that consists of a continuous two-dimensional Cu-I sheet [Cu-I = 2.5960 (14)-2.6994 (13) Å and Cu-I-Cu = 63.28 (5)-114.25 (5)°]. The cation, which lies on a mirror plane, is a typical dimethyldiphenylphosphonium ion. The structure shows a strong tendency towards segregation of the inorganic and organic parts of the structure into separate subspaces. The two-dimensional Cu-I sheet displays a pronounced subcell with pseudo-tetragonal symmetry that is broken by ordered vacancies on the Cu position. The symmetry is further reduced by the orientation of the interleaved organic counter-ion that is inclined with respect to the pseudo-mirror planes defined by the Cu-I sheet normal, perpendicular to the b axis.

Keyword
copper(I) iodide cluster structure
National Category
Chemical Sciences
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-42783 (URN)10.1107/S0108270110027149 (DOI)000280708100009 ()
Available from: 2010-09-14 Created: 2010-09-14 Last updated: 2017-12-12Bibliographically approved
5. Dual graphs realized in the compounds di-μ3-4-mercaptopyridine catena-di-μ2-iodo-di-μ3-iodo-μ4-iodo penta copper(I) and di-μ3-4-mercaptopyridine-di-catena-iodo-di-μ3-iodo tri copper(I)
Open this publication in new window or tab >>Dual graphs realized in the compounds di-μ3-4-mercaptopyridine catena-di-μ2-iodo-di-μ3-iodo-μ4-iodo penta copper(I) and di-μ3-4-mercaptopyridine-di-catena-iodo-di-μ3-iodo tri copper(I)
2010 (English)In: Journal of Solid State Chemistry, ISSN 0022-4596, E-ISSN 1095-726X, Vol. 183, no 11, 2656-2661 p.Article in journal (Refereed) Published
Abstract [en]

Two compounds, [Cu5I5](SNC5H4)2 [i] and [Cu3I3](SNC5H4)2 [ii], were synthesized under hydrothermal conditions and the crystal structures were solved. Both compounds crystallized in space group I41/a. The iodide and the sulphur from mercaptopyridine are connected to copper atom, giving the copper atoms tetrahedral coordination geometry. The pyridine end of the organic moiety is non-bonding and fills the empty space around the tetrahedra formed from copper, sulphur and iodide.

Keyword
copper iodide cluster structure
National Category
Chemical Sciences
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-42785 (URN)10.1016/j.jssc.2010.09.009 (DOI)000284179800023 ()
Available from: 2010-09-14 Created: 2010-09-14 Last updated: 2017-12-12Bibliographically approved
6. Luminescence properties of the Cu4I62- cluster
Open this publication in new window or tab >>Luminescence properties of the Cu4I62- cluster
Show others...
2011 (English)In: CrystEngComm, ISSN 1466-8033, E-ISSN 1466-8033, Vol. 13, no 14, 4729-4734 p.Article in journal (Refereed) Published
Abstract [en]

Two new solvates were prepared in the system Cu(I)I using a solvolysis reaction. The structures for both of them were solved by X-ray crystllaography, showing that they constitute two modifications of the same compound with the net formula [Cu4I6](P(C6H5)4)2·2OC(CH3)2. Both types of crystals show vivid fluorescence when exposed to UV light. The formation of the first modification (I) seems to be preferred by kinetics and on ageing in the mother liquor it converts to modification (II). The Cu positions in (I) are disordered while those in (II) are fully ordered. The luminescent properties of both crystals were characterized using a confocal microscope and an excitation wavelength of 405 nm, resulting in fluorescence spectra with the intensities of 1.22 and 0.52 relative to the reference (fluorescein 10 µM). Density functional theory calculations on the ordered Cu4I62− core of modification (II) show that the de-excitation from LUMO to HOMO is responsible for the luminescence. The calculated emission spectrum has a maximum at 531 nm in good agreement with the results from confocal microscopy.

National Category
Chemical Sciences
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-55011 (URN)10.1039/c0ce00909a (DOI)000292159200038 ()
Available from: 2011-02-24 Created: 2011-02-24 Last updated: 2017-12-11Bibliographically approved
7. Size matters - sometimes: The [CuxIy](y-x)-(NR4)+(y-yx)systems
Open this publication in new window or tab >>Size matters - sometimes: The [CuxIy](y-x)-(NR4)+(y-yx)systems
2011 (English)In: CrystEngComm, ISSN 1466-8033, E-ISSN 1466-8033, Vol. 13, 5730-5736 p.Article in journal (Refereed) Published
Abstract [en]

A systematic study of compounds formed by solvolysis of Cu in a solution of iodine in acetol in the presence of homotetraalkylammonium iodide has resulted in five new compounds: catena tetrakis(tetramethylammonium) bis(μ3-iodo)-μ2-iodo-tri-copper(I), hexakis(tetrabutylammonium) tetrakis(μ3-iodo)-tris(μ2-iodo)-di-iodo-hexa-copper(I) pentakis(μ3-iodo)-tetrakis(μ2-iodo)-di-iodo-hepta-copper(I), tris(tetrapentylammonium) μ6-iodo-bis(μ3-iodo)-hexakis(μ2-iodo)-hexa-copper(I), hexakis(tetrahexylammonium) tetrakis(μ5-iodo)-octakis(μ2-iodo)-nona-copper(I)bis(μ5-iodo)-bis(μ4-iodo)-heptakis(μ2-iodo)-octa-copper(I) and bis(tetraheptylammonium) hexakis(μ2-iodo)-tetra-copper(I). Further the previously reported compounds catena tetraethylammonium bis(μ3-iodo)-μ2-iodo-di-copper(I) and catena tetrapropylammonium tetra(μ3-iodo)-tri-copper(I) were produced by the same method. The complexity of the cuprous iodide clusters increases with increasing chain length of the counter ion. In the system with tetraheptylammonium as counter ion, the onset of crystallization was about two years! The luminescence properties that make some cuprous iodide cluster species interesting from an applications perspective are conspicuously absent in the compounds formed with the smaller tetraalkylammonium counter ions, but the compound formed with tetraheptylammonium contains the [Cu4I6]2− unit that shows vivid luminescence when exposed to UV light.

Keyword
Copper iodide cluster, crystallography
National Category
Materials Chemistry
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-55012 (URN)10.1039/C1CE05118K (DOI)000294667000021 ()
Available from: 2011-02-24 Created: 2011-02-24 Last updated: 2017-12-11Bibliographically approved
8. Luminescence properties of monoclinic Cu4I4(Piperidine)4
Open this publication in new window or tab >>Luminescence properties of monoclinic Cu4I4(Piperidine)4
2011 (English)In: Materials research bulletin, ISSN 0025-5408, E-ISSN 1873-4227, Vol. 46, no 8, 1192-1196 p.Article in journal (Refereed) Published
Abstract [en]

A new modification of Cu4I4Pip4 has been synthesized under hydrothermal conditions. X-ray crystallography revealed that this compound crystallized in the monoclinic system and consists of a tetrahedral core with composition Cu4I4, in which each Cu atom is coordinated by a piperidine molecule via the N atom. In contrast to a previously reported modification of Cu4I4Pip4, the present modification shows luminescent properties when exposed to UV-light. In addition, we have used time-dependent density functional theory calculations to characterize both compounds in term of both absorption and emission.

Place, publisher, year, edition, pages
Elsevier Ltd., 2011
Keyword
D. Luminescence
National Category
Chemical Sciences
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-55013 (URN)10.1016/j.materresbull.2011.04.012 (DOI)000292722900007 ()
Available from: 2011-02-24 Created: 2011-02-24 Last updated: 2017-12-11Bibliographically approved
9. Extended 1-D infinite chains produced in the system Cu(I)I
Open this publication in new window or tab >>Extended 1-D infinite chains produced in the system Cu(I)I
(English)Manuscript (preprint) (Other academic)
National Category
Chemical Sciences
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-55014 (URN)
Available from: 2011-02-24 Created: 2011-02-24 Last updated: 2011-02-24Bibliographically approved

Open Access in DiVA

No full text

Search in DiVA

By author/editor
Jalilian, Ehsan
By organisation
Department of Materials and Environmental Chemistry (MMK)
Materials Chemistry

Search outside of DiVA

GoogleGoogle Scholar

isbn
urn-nbn

Altmetric score

isbn
urn-nbn
Total: 563 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf