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

PDF Version Also Available for Download.

Description

This article discusses intertrimer and intratrimer metallophilic and excimeric bonding.

Physical Description

8 p.

Creation Information

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

Context

This article is part of the collection entitled: UNT Scholarly Works and was provided by UNT College of Arts and Sciences to Digital Library, a digital repository hosted by the UNT Libraries. It has been viewed 155 times , with 5 in the last month . More information about this article can be viewed below.

Who

People and organizations associated with either the creation of this article or its content.

Authors

Publisher

Provided By

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.

Contact Us

What

Descriptive information to help identify this article. Follow the links below to find similar items on the Digital Library.

Degree Information

Description

This article discusses intertrimer and intratrimer metallophilic and excimeric bonding.

Physical Description

8 p.

Notes

Reprinted with permission from the Journal of Physical Chemistry A. Copyright 2006 American Chemical Society.

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.

Source

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

Language

Item Type

Identifier

Unique identifying numbers for this article in the Digital Library or other systems.

Publication Information

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

Collections

This article is part of the following collection of related materials.

UNT Scholarly Works

Materials from the UNT community's research, creative, and scholarly activities and UNT's Open Access Repository. Access to some items in this collection may be restricted.

What responsibilities do I have when using this article?

When

Dates and time periods associated with this article.

Creation Date

  • April 8, 2006

Added to The UNT Digital Library

  • March 9, 2012, 2:17 p.m.

Description Last Updated

  • Jan. 9, 2015, 5:14 p.m.

Usage Statistics

When was this article last used?

Yesterday: 0
Past 30 days: 5
Total Uses: 155

Interact With This Article

Here are some suggestions for what to do next.

Start Reading

PDF Version Also Available for Download.

Citations, Rights, Re-Use

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.]. (digital.library.unt.edu/ark:/67531/metadc77171/: accessed April 22, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.