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 · Wed Dec 20 04:00:00 EST 1995 · Inorganic Chemistry

DOI:https://doi.org/10.1021/ic00130a004· OSTI ID:274010

Schoonover, J R ^[1]; Bates, D W; Meyer, T J ^[2]

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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, Journal Name: Inorganic Chemistry Journal Issue: 26 Vol. 34; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
ELECTRONIC STRUCTURE
EXCITED STATES
RAMAN SPECTROSCOPY
RHENIUM COMPLEXES
RUTHENIUM COMPLEXES