Structure and luminescence properties of [Re(4,7-dimethyl-1,10-phenanthroline)(CO){sub 3}py]{sup +} in a solid matrix

Journal Article · Wed May 24 00:00:00 EDT 1995 · Inorganic Chemistry

DOI:https://doi.org/10.1021/ic00115a014· OSTI ID:482583

Wallace, L ^[1]; Woods, C ^[2]; Rillema, D P ^[3]

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1. Australian National Univ., Canberra (Australia)
2. Univ. of Tennessee, Knoxville, TN (United States)
3. Univ. of North Carolina, Charlotte, NC (United States)

The low-temperature luminescence properties of [Re(4,7-Me{sub 2}phen)(CO){sub 3}py]{sup +} (4,7-Me{sub 2}phen=4,7-dimethyl-1,10-phenanthroline, py=pyridine) as a crystal or in ethanol-methanol glass are reported, together with a crystal structure of the complex as its perchlorate salt. The complex [Re(4,7-Me{sub 2}phen)(CO){sub 3}py](ClO{sub 4}) crystallizes in the space group Pna2{sub 1} with a = 16.262(4) {Angstrom}, b = 12.721(3) {Angstrom}, c = 10.814(2) {Angstrom}, and Z=4. The geometry is facial and the Re-N(4,7-Me{sub 2}phen) bond lengths are 2.13(2) and 2.24(2) {Angstrom}, the Re-N(py) bond distance is 2.15(2) {Angstrom}, and the Re-C(CO) bond distances are 1.93(3), 1.87(3), and 1.90(2) {Angstrom}. Single-crystal absorption and luminescence spectra at temperatures below 6K show that the emitting state in this environment is triplet ligand-centered ({sup 3}LC). In an ethanol-methanol glass, the luminescence spectra indicate that a largely {sup 3}LC assignment is also appropriate in this matrix; however lifetime measurements provide some evidence for a contribution from the nearby triplet metal-to-ligand charge-transfer ({sup 3}MLCT) state. Measurements of the Zeeman effect in both environments confirm these conclusions.

• Sponsoring Organization: USDOE
• OSTI ID: 482583
• Journal Information: Inorganic Chemistry, Vol. 34, Issue 11; Other Information: PBD: 24 May 1995
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
RHENIUM COMPLEXES
CRYSTAL STRUCTURE
LUMINESCENCE
ZEEMAN EFFECT