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Title: New Rh2 (II,II) Complexes for Solar Energy Applications: Panchromatic Absorption and Excited-State Reactivity

Abstract

In this work, the new heteroleptic paddlewheel complexes cis-[Rh2(μ-form)2(μ-np)2][BF4]2, where form = p-ditolylformamidinate (DTolF) or p-difluorobenzylformamidinate (F-form) and np = 1,8-napthyridyine, and cis-Rh2(μ-form)2(μ-npCOO)2 (npCOO– = 1,8-naphthyridine-2-carboxylate), were synthesized and characterized. The complexes absorb strongly throughout the ultraviolet (λmax = 300 nm, ε = 20 300 M–1 cm–1) and visible regions (λmax = 640 nm ε = 3500 M–1 cm–1), making them potentially useful new dyes with panchromatic light absorption for solar energy conversion applications. Ultrafast and nanosecond transient absorption and time-resolved infrared spectroscopies were used to characterize the identity and dynamics of the excited states, where singlet and triplet Rh2/form-to-naphthyridine, metal/ligand-to-ligand charge-transfer (ML-LCT) excited states were observed in all four complexes. The npCOO– complexes exhibit red-shifted absorption profiles extending into the near-IR and undergo photoinitiated electron transfer to generate reduced methyl viologen, a species that persists in the presence of a sacrificial donor. The energy of the triplet excited state of each complex was estimated from energy-transfer quenching experiments using a series of organic triplet donors (E(3ππ*) from 1.83 to 0.78 eV). The singlet reduction (+0.6 V vs Ag/AgCl) potentials, and singlet and triplet oxidation potentials (-1.1 and -0.5 V vs Ag/AgCl, respectively) were determined. Finally, based on the excited-statemore » lifetimes and redox properties, these complexes represent a new class of light absorbers with potential application as dyes for charge injection into semiconductor solar cells and in sensitizer-catalyst assemblies for photocatalysis that operate with irradiation from the ultraviolet to ~800 nm.« less

Authors:
 [1];  [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1]
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  1. The Ohio State Univ., Columbus, OH (United States). Department of Chemistry and Biochemistry
Publication Date:
Research Org.:
The Ohio State Univ., Columbus, OH (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1430209
Grant/Contract Number:  
SC0010542
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 41; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Dirhodium; naphthyridine; light absorption; time-resolved; excited state; infrared spectroscopy

Citation Formats

Whittemore, Tyler J., Sayre, Hannah J., Xue, Congcong, White, Travis A., Gallucci, Judith C., and Turro, Claudia. New Rh2 (II,II) Complexes for Solar Energy Applications: Panchromatic Absorption and Excited-State Reactivity. United States: N. p., 2017. Web. doi:10.1021/jacs.7b08489.
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Whittemore, Tyler J., Sayre, Hannah J., Xue, Congcong, White, Travis A., Gallucci, Judith C., & Turro, Claudia. New Rh2 (II,II) Complexes for Solar Energy Applications: Panchromatic Absorption and Excited-State Reactivity. United States. https://doi.org/10.1021/jacs.7b08489
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Whittemore, Tyler J., Sayre, Hannah J., Xue, Congcong, White, Travis A., Gallucci, Judith C., and Turro, Claudia. Wed . "New Rh2 (II,II) Complexes for Solar Energy Applications: Panchromatic Absorption and Excited-State Reactivity". United States. https://doi.org/10.1021/jacs.7b08489. https://www.osti.gov/servlets/purl/1430209.
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@article{osti_1430209,
title = {New Rh2 (II,II) Complexes for Solar Energy Applications: Panchromatic Absorption and Excited-State Reactivity},
author = {Whittemore, Tyler J. and Sayre, Hannah J. and Xue, Congcong and White, Travis A. and Gallucci, Judith C. and Turro, Claudia},
abstractNote = {In this work, the new heteroleptic paddlewheel complexes cis-[Rh2(μ-form)2(μ-np)2][BF4]2, where form = p-ditolylformamidinate (DTolF) or p-difluorobenzylformamidinate (F-form) and np = 1,8-napthyridyine, and cis-Rh2(μ-form)2(μ-npCOO)2 (npCOO– = 1,8-naphthyridine-2-carboxylate), were synthesized and characterized. The complexes absorb strongly throughout the ultraviolet (λmax = 300 nm, ε = 20 300 M–1 cm–1) and visible regions (λmax = 640 nm ε = 3500 M–1 cm–1), making them potentially useful new dyes with panchromatic light absorption for solar energy conversion applications. Ultrafast and nanosecond transient absorption and time-resolved infrared spectroscopies were used to characterize the identity and dynamics of the excited states, where singlet and triplet Rh2/form-to-naphthyridine, metal/ligand-to-ligand charge-transfer (ML-LCT) excited states were observed in all four complexes. The npCOO– complexes exhibit red-shifted absorption profiles extending into the near-IR and undergo photoinitiated electron transfer to generate reduced methyl viologen, a species that persists in the presence of a sacrificial donor. The energy of the triplet excited state of each complex was estimated from energy-transfer quenching experiments using a series of organic triplet donors (E(3ππ*) from 1.83 to 0.78 eV). The singlet reduction (+0.6 V vs Ag/AgCl) potentials, and singlet and triplet oxidation potentials (-1.1 and -0.5 V vs Ag/AgCl, respectively) were determined. Finally, based on the excited-state lifetimes and redox properties, these complexes represent a new class of light absorbers with potential application as dyes for charge injection into semiconductor solar cells and in sensitizer-catalyst assemblies for photocatalysis that operate with irradiation from the ultraviolet to ~800 nm.},
doi = {10.1021/jacs.7b08489},
journal = {Journal of the American Chemical Society},
number = 41,
volume = 139,
place = {United States},
year = {2017},
month = {10}
}
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https://doi.org/10.1021/jacs.7b08489
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Figure 1 Figure 1: Molecular structures of 1 – 4.
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    Electron injection into titanium dioxide by panchromatic dirhodium photosensitizers with low energy red light
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    • Chemical Communications, Vol. 55, Issue 70
    • DOI: 10.1039/c9cc04677a
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