Luminescent Photofragments of (1,1,1,5,5,5-Hexafluoro-2,4-pentanedionato) Metal Complexes in the Gas Phase

David Talaga, Stephen D. Hanna, Jeffrey I. Zink

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Abstract

The luminescence that is observed under gas phase photolytic deposition conditions is studied for Cr(hfac)3, Ni(hfac)2, and Pt(hfac)2. This luminescence is analyzed under a variety of conditions, including the relatively high pressures of an evacuated gas cell and the collision-free conditions of a molecular beam. The effects of inert buffer gas are also studied. Features in these spectra indicate that, in general, multiple photolysis processes occur. Some simple fragments that are produced from these compounds are identified, including bare metal atoms (Ni, Cr), metal monofluorides (NiF, CrF), CH (in the case of Ni(hfac)2), and metal carbide from Pt(hfac)2. It is postulated that the difference in the observed photofragmentation pathway in the case of platinum is due to σ bonding to the β carbon of the hfac moiety as opposed to the bidentate bonding of the other two metals. Possible mechanisms are presented. Detailed analysis of the spectra allows characterization of the internal energy of the platinum carbide photofragment.

Original languageEnglish
Pages (from-to)2880-2887
Number of pages8
JournalInorganic Chemistry
Volume37
Issue number12
StatePublished - 1 Dec 1998

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Coordination Complexes
Gases
Metals
vapor phases
Platinum
carbides
metals
Carbides
Luminescence
platinum
luminescence
Molecular beams
Photolysis
internal energy
gases
molecular beams
photolysis
Buffers
Carbon
buffers

Cite this

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title = "Luminescent Photofragments of (1,1,1,5,5,5-Hexafluoro-2,4-pentanedionato) Metal Complexes in the Gas Phase",
abstract = "The luminescence that is observed under gas phase photolytic deposition conditions is studied for Cr(hfac)3, Ni(hfac)2, and Pt(hfac)2. This luminescence is analyzed under a variety of conditions, including the relatively high pressures of an evacuated gas cell and the collision-free conditions of a molecular beam. The effects of inert buffer gas are also studied. Features in these spectra indicate that, in general, multiple photolysis processes occur. Some simple fragments that are produced from these compounds are identified, including bare metal atoms (Ni, Cr), metal monofluorides (NiF, CrF), CH (in the case of Ni(hfac)2), and metal carbide from Pt(hfac)2. It is postulated that the difference in the observed photofragmentation pathway in the case of platinum is due to σ bonding to the β carbon of the hfac moiety as opposed to the bidentate bonding of the other two metals. Possible mechanisms are presented. Detailed analysis of the spectra allows characterization of the internal energy of the platinum carbide photofragment.",
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Luminescent Photofragments of (1,1,1,5,5,5-Hexafluoro-2,4-pentanedionato) Metal Complexes in the Gas Phase. / Talaga, David; Hanna, Stephen D.; Zink, Jeffrey I.

In: Inorganic Chemistry, Vol. 37, No. 12, 01.12.1998, p. 2880-2887.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Luminescent Photofragments of (1,1,1,5,5,5-Hexafluoro-2,4-pentanedionato) Metal Complexes in the Gas Phase

AU - Talaga, David

AU - Hanna, Stephen D.

AU - Zink, Jeffrey I.

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N2 - The luminescence that is observed under gas phase photolytic deposition conditions is studied for Cr(hfac)3, Ni(hfac)2, and Pt(hfac)2. This luminescence is analyzed under a variety of conditions, including the relatively high pressures of an evacuated gas cell and the collision-free conditions of a molecular beam. The effects of inert buffer gas are also studied. Features in these spectra indicate that, in general, multiple photolysis processes occur. Some simple fragments that are produced from these compounds are identified, including bare metal atoms (Ni, Cr), metal monofluorides (NiF, CrF), CH (in the case of Ni(hfac)2), and metal carbide from Pt(hfac)2. It is postulated that the difference in the observed photofragmentation pathway in the case of platinum is due to σ bonding to the β carbon of the hfac moiety as opposed to the bidentate bonding of the other two metals. Possible mechanisms are presented. Detailed analysis of the spectra allows characterization of the internal energy of the platinum carbide photofragment.

AB - The luminescence that is observed under gas phase photolytic deposition conditions is studied for Cr(hfac)3, Ni(hfac)2, and Pt(hfac)2. This luminescence is analyzed under a variety of conditions, including the relatively high pressures of an evacuated gas cell and the collision-free conditions of a molecular beam. The effects of inert buffer gas are also studied. Features in these spectra indicate that, in general, multiple photolysis processes occur. Some simple fragments that are produced from these compounds are identified, including bare metal atoms (Ni, Cr), metal monofluorides (NiF, CrF), CH (in the case of Ni(hfac)2), and metal carbide from Pt(hfac)2. It is postulated that the difference in the observed photofragmentation pathway in the case of platinum is due to σ bonding to the β carbon of the hfac moiety as opposed to the bidentate bonding of the other two metals. Possible mechanisms are presented. Detailed analysis of the spectra allows characterization of the internal energy of the platinum carbide photofragment.

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