Skip to main content
Journal cover image

Evaluating the extent of intramolecular charge transfer in the excited states of rhenium(I) donor-acceptor complexes with time-resolved vibrational spectroscopy.

Publication ,  Journal Article
Yue, Y; Grusenmeyer, T; Ma, Z; Zhang, P; Pham, TT; Mague, JT; Donahue, JP; Schmehl, RH; Beratan, DN; Rubtsov, IV
Published in: The journal of physical chemistry. B
December 2013

Excited states in transition-metal complexes, even in those featuring ligands with strong electron donating and accepting properties, often involve only partial charge transfer between the donor and acceptor ligands. The excited-state properties of [Re(bpy)(CO)3L](+) compounds were studied, where L is 4-dimethylaminobenzonitrile (Re4DMABN), 3-dimethylaminobenzonitrile (Re3DMABN), and benzonitrile (ReBN) using time-resolved infrared (TRIR) and electronic spectroscopy methods as well as electronic structure computations. The DMABN complexes exhibit strongly solvent-dependent luminescence; the excited state lifetime decreases from microseconds in dichloromethane to several nanoseconds in mixed MeOH:DCM (1:1) solvent. Despite the similarities in the solvent dependence of the excited state dynamics and redox properties for Re3DMABN and Re4DMABN, the nature of the lowest energy excited states formed in these two compounds is drastically different. For example, the lowest energy excited state for Re4DMABN in the mixed solvent is assigned to the (4DMABN → bpy) ligand-to-ligand charge transfer (LLCT) state featuring partial charge transfer character. An equilibrium between a 3DMABN intraligand triplet ((3)IL) and a metal-ligand-to-ligand charge transfer (MLLCT) state is found for Re3DMABN in the mixed solvent with the latter at ca. 400 cm(-1) lower energy. The origin of such a drastic difference between the states involved in Re4DMABN and Re3DMABN is attributed to a difference in the energies of polarized quinoidal resonance structures in 4DMABN and 3DMABN ligands.

Duke Scholars

Published In

The journal of physical chemistry. B

DOI

EISSN

1520-5207

ISSN

1520-6106

Publication Date

December 2013

Volume

117

Issue

49

Start / End Page

15903 / 15916

Related Subject Headings

  • Time Factors
  • Spectrophotometry, Infrared
  • Solvents
  • Rhenium
  • Quantum Theory
  • Nitriles
  • Electrons
  • Coordination Complexes
  • 51 Physical sciences
  • 40 Engineering
 

Citation

APA
Chicago
ICMJE
MLA
NLM
Yue, Y., Grusenmeyer, T., Ma, Z., Zhang, P., Pham, T. T., Mague, J. T., … Rubtsov, I. V. (2013). Evaluating the extent of intramolecular charge transfer in the excited states of rhenium(I) donor-acceptor complexes with time-resolved vibrational spectroscopy. The Journal of Physical Chemistry. B, 117(49), 15903–15916. https://doi.org/10.1021/jp409628e
Yue, Yuankai, Tod Grusenmeyer, Zheng Ma, Peng Zhang, Tri Tat Pham, Joel T. Mague, James P. Donahue, Russell H. Schmehl, David N. Beratan, and Igor V. Rubtsov. “Evaluating the extent of intramolecular charge transfer in the excited states of rhenium(I) donor-acceptor complexes with time-resolved vibrational spectroscopy.The Journal of Physical Chemistry. B 117, no. 49 (December 2013): 15903–16. https://doi.org/10.1021/jp409628e.
Yue Y, Grusenmeyer T, Ma Z, Zhang P, Pham TT, Mague JT, et al. Evaluating the extent of intramolecular charge transfer in the excited states of rhenium(I) donor-acceptor complexes with time-resolved vibrational spectroscopy. The journal of physical chemistry B. 2013 Dec;117(49):15903–16.
Yue, Yuankai, et al. “Evaluating the extent of intramolecular charge transfer in the excited states of rhenium(I) donor-acceptor complexes with time-resolved vibrational spectroscopy.The Journal of Physical Chemistry. B, vol. 117, no. 49, Dec. 2013, pp. 15903–16. Epmc, doi:10.1021/jp409628e.
Yue Y, Grusenmeyer T, Ma Z, Zhang P, Pham TT, Mague JT, Donahue JP, Schmehl RH, Beratan DN, Rubtsov IV. Evaluating the extent of intramolecular charge transfer in the excited states of rhenium(I) donor-acceptor complexes with time-resolved vibrational spectroscopy. The journal of physical chemistry B. 2013 Dec;117(49):15903–15916.
Journal cover image

Published In

The journal of physical chemistry. B

DOI

EISSN

1520-5207

ISSN

1520-6106

Publication Date

December 2013

Volume

117

Issue

49

Start / End Page

15903 / 15916

Related Subject Headings

  • Time Factors
  • Spectrophotometry, Infrared
  • Solvents
  • Rhenium
  • Quantum Theory
  • Nitriles
  • Electrons
  • Coordination Complexes
  • 51 Physical sciences
  • 40 Engineering