Competition between ligand centered and charge transfer lowest excited states in bis cyclometalated Rh3+ and Ir3+ complexes View Full Text


Ontology type: schema:Chapter     


Chapter Info

DATE

1994

AUTHORS

Mirco G. Colombo , Andreas Hauser , Hans U. Güdel

ABSTRACT

In this article the results of a detailed optical spectroscopic investigation of a series of related bis-cyclometalated Rh3+ and Ir3+ complexes of the general formula [M(C∩N)2N∩N]+, M=Rh3+, Ir3+ (HC∩N=2-phenylpyridine or 2-(2-thienyl) pyridine; N∩N-2,2′-bipyridine or ethylenediamine) are summarized. The nature of the lowest excited states of the compounds is discussed on the basis of their absorption, luminescence and luminescence line narrowing spectra in solutions and glasses at temperatures from 10 K to 300 K, whereas for the characterization of higher excited states single crystal absorption spectra and excitation spectra of polycrystalline samples are used. In the Rh3+ complexes the lowest excited states correspond to a 3π-π* transition localized on the cyclometalating ligands, whereas in the Ir3+ complexes, depending on the environment, either a 3π-π* or a metal to ligand charge transfer (3MLCT) excited state is lowest in energy. The pronounced solvatochromic and rigidochromic effects of the Ir3+ compounds are responsible for the reversal of the order of the lowest excited states. Mixing between the π-π* and MLCT excited states is reflected in the oscillator strengths, luminescence lifetimes, vibrational structure and zero field splittings. The phenomenon of dual luminescence is attributed to a large inhomogeneous distribution of sites in solution and glasses. More... »

PAGES

143-171

Identifiers

URI

http://scigraph.springernature.com/pub.10.1007/3-540-58155-3_5

DOI

http://dx.doi.org/10.1007/3-540-58155-3_5

DIMENSIONS

https://app.dimensions.ai/details/publication/pub.1016051863


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