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Title: Application of resonance Raman spectroscopy to electronic structure in metal complex excited states. Excited-state ordering and electron delocalization in dipyrido[3,2-a: 2`,3`-c] phenazine (dppz): Complexes of Re(I) and Ru(II)

Journal Article · · Inorganic Chemistry
 [1]; ;  [2]
  1. Los Alamos National Laboratory, Los Alamos, NM (United States)
  2. Uinv. of North Carolina, Chapel Hill, NC (United States)

Excited-state ordering and electron delocalization in Dipyrido[3,2-a:2`,3`-c]phenazine (dppz): Complexes of Re(I) and Ru(II). From excitation-dependent, resonance Raman measurements on [Ru(dmb){sub 2}(dppz)]{sup 2+} (dmp is ,4`-dimethyl-2,2`-bipyridine; dppz is dipyrido [3,2-a:2`,3`-c]phenazine) in CH{sub 3}CN a metal-to-metal ligand charge transfer (MLCT) band at 450 nm is Ru{sup II} (d{pi}){r_arrow} dmb ({pi}){sup *} in character with Ru{sup II}(d{pi}){r_arrow}dppz ({pi}){sup *} appearing as a shoulder at {approx} 490 ligand and point to delocalization of the excited electron over the entire ligand framework. From transient resonance Raman measurements on fac-[Re(dppz)(CO){sub 3-}(PPh{sub 3})] + (PPh{sub 3} is triphenylphosphine) and fac-[Re(dppz)(CO){sub 3-}Cl], the lowest excited state in both is dppz-localized {sup 3}{pi}{pi}{sup *} in character even though the chloro complex is a MLCT emitter.

Sponsoring Organization:
USDOE
OSTI ID:
274010
Journal Information:
Inorganic Chemistry, Vol. 34, Issue 26; Other Information: PBD: 20 Dec 1995
Country of Publication:
United States
Language:
English