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Title: Ultrafast interligand electron transfer in cis -[Ru(4,4′-dicarboxylate-2,2′-bipyridine) 2 (NCS) 2 ] 4− and implications for electron injection limitations in dye sensitized solar cells

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/C8SC00274F· OSTI ID:1467930
 [1]; ORCiD logo [1];  [1]; ORCiD logo [2];  [1];  [3];  [3]; ORCiD logo [3]; ORCiD logo [1]
  1. Department of Chemistry – Ångström Laboratory, Uppsala University, SE75120 Uppsala, Sweden
  2. Department of Chemistry – Ångström Laboratory, Uppsala University, SE75120 Uppsala, Sweden, Department of Biotechnology
  3. Department of Chemistry, Argonne-Northwestern Solar Energy Research (ANSER) Center, Northwestern University, Evanston, USA
+ Show Author Affiliations

Interligand electron transfer (ILET) of the lowest metal-to-ligand charge transfer (MLCT) state of N712 (cis-[Ru(dcb)2(NCS)2]4–, where dcb = 4,4'-dicarboxylate-2,2'-bipyridine) in a deuterated acetonitrile solution has been studied by means of femtosecond transient absorption anisotropy in the mid-IR. Time-independent B3LYP density functional calculations were performed to assign vibrational bands and determine their respective transition dipole moments. The transient absorption spectral band at 1327 cm–1, assigned to a symmetric carboxylate stretch, showed significant anisotropy. A rapid anisotropy increase (τ1 ≈ 2 ps) was tentatively assigned to vibrational and solvent relaxation, considering the excess energy available after the excited singlet–triplet conversion. Thereafter, the anisotropy decayed to zero with a time constant τ2 ≈ 240 ps, which was assigned to the rotational correlation time of the complex in deuterated acetonitrile. No other distinctive changes to the anisotropy were observed and the amplitude of the slow component at time zero agrees well with that predicted for a random mixture of MLCT localization on either of the two dcb ligands. The results therefore suggest that MLCT randomization over the two dcb ligands occurs on the sub-ps time scale. This is much faster than proposed by previous reports on the related N3 complex [Benkö et al., J. Phys. Chem. B, 2004, 108, 2862, and Waterland et al., J. Phys. Chem. A, 2001, 105, 4019], but in agreement with that found by Wallin and co-workers [J. Phys. Chem. A, 2005, 109, 4697] for the [Ru(bpy)3]2+ (bpy = 2,2'-bipyridine) complex. This suggests that electron injection from the excited dye into TiO2 in dye-sensitized solar cells is not limited by ILET.

Research Organization:
Northwestern Univ., Evanston, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Light Energy Activated Redox Processes (LEAP)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Knut and Alice Wallenberg Foundation; Swedish Energy Agency
Grant/Contract Number:
SC0001059; 43599-1
OSTI ID:
1467930
Alternate ID(s):
OSTI ID: 1566640
Journal Information:
Chemical Science, Journal Name: Chemical Science Vol. 9 Journal Issue: 41; ISSN 2041-6520
Publisher:
Royal Society of Chemistry (RSC)Copyright Statement
Country of Publication:
United Kingdom
Language:
English
Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

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  • Youngblood, W. Justin; Lee, Seung-Hyun Anna; Kobayashi, Yoji
  • Journal of the American Chemical Society, Vol. 131, Issue 3, p. 926-927 https://doi.org/10.1021/ja809108y
journal January 2009
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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
catalysis (homogeneous)
catalysis (heterogeneous)
solar (photovoltaic)
solar (fuels)
optics
phonons
photosynthesis (natural and artificial)
bio-inspired
hydrogen and fuel cells
charge transport
magnetism and spin physics
materials and chemistry by design
mesostructured materials
synthesis (novel materials)
synthesis (self-assembly)
synthesis (scalable processing)