| Description: | This article discusses three-coordinate Au(I) phosphine complexes. Abstract: DFT calculations were used to optimize the phosphorescent excited state of three-coordinate [Au(PR3)3]+ complexes. The results indicate that the complexes rearrange from their singlet ground-state trigonal planar geometry to a T-shape in the lowest triplet luminescent excited state. The optimized structure of the exciton contradicts the structure predicted based on the AuP bonding properties of the ground-state HOMO and LUMO. The rearrangement to T-shape is a Jahn-Teller distortion because an electron is taken from the degenerate e' (5dxy, 5dx2-y2) orbital upon photoexcitation of the ground-state D3h complex. The calculated UV absorption and visible emission energies are consistent with the experimental data and explain the large Stokes' shifts while such correlations are not possible in optimized models that constrained the exciton to the ground-state trigonal geometry. |
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| Creator(s): | |
| Creation Date: | November 4, 2003 |
| Partner(s): |
UNT College of Arts and Sciences
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| Collection(s): |
UNT Scholarly Works
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| Usage: |
Total Uses: 37
Past 30 days: 1
Yesterday: 0
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| Creator (Author): |
Barakat, Khaldoon A.
University of North Texas |
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| Creator (Author): |
Cundari, Thomas R., 1964-
University of North Texas |
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| Creator (Author): |
Omary, Mohammad A.
University of North Texas |
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| Publisher Info: |
Publisher Name: American Chemical Society
Place of Publication: [Washington, DC]
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| Date(s): |
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| Description: | This article discusses three-coordinate Au(I) phosphine complexes. Abstract: DFT calculations were used to optimize the phosphorescent excited state of three-coordinate [Au(PR3)3]+ complexes. The results indicate that the complexes rearrange from their singlet ground-state trigonal planar geometry to a T-shape in the lowest triplet luminescent excited state. The optimized structure of the exciton contradicts the structure predicted based on the AuP bonding properties of the ground-state HOMO and LUMO. The rearrangement to T-shape is a Jahn-Teller distortion because an electron is taken from the degenerate e' (5dxy, 5dx2-y2) orbital upon photoexcitation of the ground-state D3h complex. The calculated UV absorption and visible emission energies are consistent with the experimental data and explain the large Stokes' shifts while such correlations are not possible in optimized models that constrained the exciton to the ground-state trigonal geometry. |
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| Degree: |
Department:
Chemistry
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| Note: |
Reprinted with permission from the Journal of the American Chemical Society. Copyright 2003 American Chemical Society. |
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| Physical Description: |
2 p. |
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| Keyword(s): | phosphine complexes | transition metal complexes | |
| Source: | Journal of the American Chemical Society, 2003, Washington DC: American Chemical Society, pp. 14228-14229 | |
| Partner: |
UNT College of Arts and Sciences
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| Collection: |
UNT Scholarly Works
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| Resource Type: | Article | |
| Format: | Text | |
| Rights: |
Access:
Public
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| Citation: |
Publication Title: Journal of the American Chemical Society
Volume: 125
Issue: 47
Page Start: 14228
Page End: 14229
Peer Reviewed: Yes
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