Intertrimer and Intratrimer Metallophilic and Excimeric Bonding in the Ground and Phosphorescent States of Trinuclear Coinage Metal Pyrazolates: A Computational Study

Grimes, Thomas V.; Omary, Mohammad A.; Dias, H. V. Rasika; Cundari, Thomas R., 1964-

doi:10.1021/jp0605146

Intertrimer and Intratrimer Metallophilic and Excimeric Bonding in the Ground and Phosphorescent States of Trinuclear Coinage Metal Pyrazolates: A Computational Study

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This article discusses intertrimer and intratrimer metallophilic and excimeric bonding.

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8 p.

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Grimes, Thomas V.; Omary, Mohammad A.; Dias, H. V. Rasika & Cundari, Thomas R., 1964- April 8, 2006.

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This article is part of the collection entitled: UNT Scholarly Works and was provided by the UNT College of Arts and Sciences to the UNT Digital Library, a digital repository hosted by the UNT Libraries. It has been viewed 250 times. More information about this article can be viewed below.

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Grimes, Thomas V. University of North Texas
Omary, Mohammad A. University of North Texas
Dias, H. V. Rasika University of Texas at Arlington
Cundari, Thomas R., 1964- University of North Texas

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American Chemical Society
Place of Publication: [Washington, D.C.]

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UNT College of Arts and Sciences

The UNT College of Arts and Sciences educates students in traditional liberal arts, performing arts, sciences, professional, and technical academic programs. In addition to its departments, the college includes academic centers, institutes, programs, and offices providing diverse courses of study.

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Department: Chemistry
Department: Center for Advanced Scientific Computing and Modeling

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This article discusses intertrimer and intratrimer metallophilic and excimeric bonding.

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8 p.

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Abstract: The interactions present in cyclic trinuclear coinage metal pyrazolates were studied computationally. Cuprophilic interaction was found to bind the singlet ground state of the dimer of trimers {[Cu(Pz)]₃}₂, overcoming electrostatic repulsion. The large variation in intertrimer separations found in the literature for coinage metal pyrazolates is consistent with the relatively weak metallophilic interaction. The emissive triplet excited-state geometry of {[M(Pz]₃}₂ is predicted by density functional calculations to show major geometric distortion caused by Jahn-Teller instability and excimeric M-M bonding. Large calculated Stokes' shifts, which are also observed for experimental models, are consistent with significant excited-state distortions for these materials. The major finding derived from the present study is that the intertrimer M⋯M contraction in the emissive T₁ state is much more than the intratrimer contraction in all {[M(Pz)]₃}₂ models, giving rise to a lower T₁ → S₀ phosphorescence energy in these models than in analogous monomer-of-trimer models. The observations made here point to a great potential for rationally tuning the emission properties of trinuclear coinage metal complexes through choice of the metal and ligands.

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Journal of Physical Chemistry A, 2006, Washington D.C.: American Chemical Society, pp. 5823-5830

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English

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https://doi.org/10.1021/jp0605146
Archival Resource Key: ark:/67531/metadc77171

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Publication Title: Journal of Physical Chemistry A
Volume: 110
Page Start: 5823
Page End: 5830
Pages: 8
Peer Reviewed: Yes

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April 8, 2006

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March 9, 2012, 2:17 p.m.

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Grimes, Thomas V.; Omary, Mohammad A.; Dias, H. V. Rasika & Cundari, Thomas R., 1964-. Intertrimer and Intratrimer Metallophilic and Excimeric Bonding in the Ground and Phosphorescent States of Trinuclear Coinage Metal Pyrazolates: A Computational Study, article, April 8, 2006; [Washington, D.C.]. (https://digital.library.unt.edu/ark:/67531/metadc77171/: accessed September 26, 2023), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; crediting UNT College of Arts and Sciences.

Intertrimer and Intratrimer Metallophilic and Excimeric Bonding in the Ground and Phosphorescent States of Trinuclear Coinage Metal Pyrazolates: A Computational Study

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