Pronounced photosensitivity of molecular [Ru(bpy)<sub>2</sub>(OSO)]<sup>+</sup> solutions based on two photoinduced linkage isomers

doi:10.1364/OE.17.015052

Pronounced photosensitivity of molecular [Ru(bpy)₂(OSO)]⁺ solutions based on two photoinduced linkage isomers

Volker Dieckmann, Sebastian Eicke, Jeffrey J. Rack, Theo Woike, and Mirco Imlau »View Author Affiliations

Optics Express, Vol. 17, Issue 17, pp. 15052-15060 (2009)
http://dx.doi.org/10.1364/OE.17.015052

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Abstract

Photosensitive properties of [Ru(bpy)₂(OSO)] ∙ PF₆ dissolved in propylene carbonate originating from photoinduced linkage isomerism have been studied by temperature and exposure dependent transmission and UV/Vis absorption spectroscopy. An exceeding photochromic photosensitivity of S = (63 ± 10) × 10³ cm l J⁻¹ mol⁻¹ is determined. It is attributed to a maximum population of 100% molecules in the photoinduced isomers, a unique absorption cross section per molecule and a very low light exposure of Q₀ = (0.25 ± 0.03) Ws cm⁻² for isomerism. Relaxation studies of O-bonded to S-bonded isomers at different temperatures verify the existence of two distinct structures of linkage isomers determined by the activation energies of E_A,1 = (0.76 ± 0.08) eV and E_A,2 = (1.00 ± 0.14) eV.

OCIS Codes
(160.4670) Materials : Optical materials
(260.5130) Physical optics : Photochemistry
(300.6550) Spectroscopy : Spectroscopy, visible
(160.5335) Materials : Photosensitive materials

ToC Category:
Materials

History
Original Manuscript: June 10, 2009
Revised Manuscript: July 23, 2009
Manuscript Accepted: July 25, 2009
Published: August 10, 2009

Citation
Volker Dieckmann, Sebastian Eicke, Jeffrey J. Rack, Theo Woike, and Mirco Imlau, "Pronounced photosensitivity of molecular [Ru(bpy)₂(OSO)]⁺ solutions based on two photoinduced linkage isomers," Opt. Express 17, 15052-15060 (2009)
http://www.opticsinfobase.org/oe/abstract.cfm?URI=oe-17-17-15052

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References

P. Gütlich, Y. Garcia, and Th. Woike, “Photoswitchable coordination compounds,” Coord. Chem. Rev. 219, 839–879 (2001). [CrossRef]
P. Coppens, I. Novozhilova, and A. Kovalevsky, “Photoinduced linkage isomers of transition-metal nitrosyl compounds and related complexes,” Chem. Rev. 102(4), 861–884 (2002). [CrossRef] [PubMed]
Th. Woike, S. Haussühl, B. Sugg, R. A. Rupp, J. Beckers, M. Imlau, and R. Schieder, “Phase gratings in the visible and near-infrared spectral range realized by metastable electronic states in Na2[Fe(CN)5NO]∙2H2O,” Appl. Phys. B 63, 243–248 (1996).
M. Imlau, S. Haussühl, Th. Woike, R. Schieder, V. Angelov, R. A. Rupp, and K. Schwarz, “Holographic recording by excitation of metastable electronic states in Na2[Fe(CN)5NO]∙2H2O: a new photorefractive effect,” Appl. Phys. B 68, 877–885 (1999). [CrossRef]
J. J. Rack, “Photoinduced molecular switches,” U.S. patent 6,433,270 (2002)
D. Schaniel, Th. Woike, C. Merschjann, and M. Imlau, “Transient kinetics of light-induced metastable states in single crystals and aqueous solutions of Na2[Fe(CN)5NO]∙2H2O,” Phys. Rev. B 72(19), 195119 (2005). [CrossRef]
D. Psaltis, S. R. Quake, and C. H. Yang, “Developing optofluidic technology through the fusion of microfluidics and optics,” Nature 442(7101), 381–386 (2006). [CrossRef] [PubMed]
D. Schaniel, B. Cormary, I. Malfant, L. Valade, Th. Woike, B. Delley, K. W. Kramer, and H. U. Güdel, “Generation of one light-induced metastable nitrosyl linkage isomer in [Pt(NH3)4Cl(NO)]Cl2 in the red spectral range,” Phys. Chem. Chem. Phys. 9(28), 3717–3724 (2007). [CrossRef] [PubMed]
D. Schaniel, M. Imlau, T. Weisemoeller, Th. Woike, K. W. Kramer, and H. U. Güdel, “Photoinduced Nitrosyl Linkage Isomers Uncover a Variety of Unconventional Photorefractive Media,” Adv. Mater. 19(5), 723–726 (2007). [CrossRef]
D. P. Butcher, A. A. Rachford, J. L. Petersen, and J. J. Rack, “Phototriggered S --> O isomerization of a ruthenium-bound chelating sulfoxide,” Inorg. Chem. 45(23), 9178–9180 (2006). [CrossRef] [PubMed]
B. A. McClure, N. V. Mockus, D. P. Butcher, D. A. Lutterman, C. Turro, J. L. Petersen, and J. J. Rack, “Photochromic Ruthenium Sulfoxide Complexes: Evidence for Isomerization Through a Conical Intersection,” Inorg. Chem. (accepted). [PubMed]
M. J. Root and E. Deutsch, “Synthesis and Characterization of (Bipyridine)(terpyridine)(chalcogenoether)ruthenium(II) Complexes - Kinetics and Mechanism of the Hydrogen Peroxide Oxidation of [(bpy)(tpy)RuS(CH3)2]2+ to [(bpy)(tpy)RuS(O)(CH3)2]2+. Kinetics of the Aquation of [(bpy)(tpy)RuS(O)(CH3)2]2+,” Inorg. Chem. 24(10), 1464–1471 (1985). [CrossRef]
P. Günter, “Holography, coherent light amplification and optical phase conjugation with photorefractive materials,” Phys. Rep. 93(4), 199–299 (1982). [CrossRef]
A. A. Rachford, J. L. Petersen, and J. J. Rack, “Designing molecular bistability in ruthenium dimethyl sulfoxide complexes,” Inorg. Chem. 44(22), 8065–8075 (2005). [CrossRef] [PubMed]

Angelov, V.
Beckers, J.
Butcher, D. P.
Coppens, P.
Cormary, B.
Delley, B.
Deutsch, E.
Garcia, Y.
Güdel, H. U.
Günter, P.
Gütlich, P.
Haussühl, S.
Imlau, M.
Kovalevsky, A.
Kramer, K. W.
Lutterman, D. A.
Malfant, I.
McClure, B. A.
Merschjann, C.
Mockus, N. V.
Novozhilova, I.
Petersen, J. L.
Psaltis, D.
Quake, S. R.
Rachford, A. A.
Rack, J. J.
Root, M. J.
Rupp, R. A.
Schaniel, D.
Schieder, R.
Schwarz, K.
Sugg, B.
Turro, C.
Valade, L.
Weisemoeller, T.
Woike, Th.
Yang, C. H.

Adv. Mater.

D. Schaniel, M. Imlau, T. Weisemoeller, Th. Woike, K. W. Kramer, and H. U. Güdel, “Photoinduced Nitrosyl Linkage Isomers Uncover a Variety of Unconventional Photorefractive Media,” Adv. Mater. 19(5), 723–726 (2007). [CrossRef]

Appl. Phys. B

Th. Woike, S. Haussühl, B. Sugg, R. A. Rupp, J. Beckers, M. Imlau, and R. Schieder, “Phase gratings in the visible and near-infrared spectral range realized by metastable electronic states in Na2[Fe(CN)5NO]∙2H2O,” Appl. Phys. B 63, 243–248 (1996).
M. Imlau, S. Haussühl, Th. Woike, R. Schieder, V. Angelov, R. A. Rupp, and K. Schwarz, “Holographic recording by excitation of metastable electronic states in Na2[Fe(CN)5NO]∙2H2O: a new photorefractive effect,” Appl. Phys. B 68, 877–885 (1999). [CrossRef]

Chem. Rev.

P. Coppens, I. Novozhilova, and A. Kovalevsky, “Photoinduced linkage isomers of transition-metal nitrosyl compounds and related complexes,” Chem. Rev. 102(4), 861–884 (2002). [CrossRef] [PubMed]

Coord. Chem. Rev.

P. Gütlich, Y. Garcia, and Th. Woike, “Photoswitchable coordination compounds,” Coord. Chem. Rev. 219, 839–879 (2001). [CrossRef]

Inorg. Chem.

D. P. Butcher, A. A. Rachford, J. L. Petersen, and J. J. Rack, “Phototriggered S --> O isomerization of a ruthenium-bound chelating sulfoxide,” Inorg. Chem. 45(23), 9178–9180 (2006). [CrossRef] [PubMed]
B. A. McClure, N. V. Mockus, D. P. Butcher, D. A. Lutterman, C. Turro, J. L. Petersen, and J. J. Rack, “Photochromic Ruthenium Sulfoxide Complexes: Evidence for Isomerization Through a Conical Intersection,” Inorg. Chem. (accepted). [PubMed]
M. J. Root and E. Deutsch, “Synthesis and Characterization of (Bipyridine)(terpyridine)(chalcogenoether)ruthenium(II) Complexes - Kinetics and Mechanism of the Hydrogen Peroxide Oxidation of [(bpy)(tpy)RuS(CH3)2]2+ to [(bpy)(tpy)RuS(O)(CH3)2]2+. Kinetics of the Aquation of [(bpy)(tpy)RuS(O)(CH3)2]2+,” Inorg. Chem. 24(10), 1464–1471 (1985). [CrossRef]
A. A. Rachford, J. L. Petersen, and J. J. Rack, “Designing molecular bistability in ruthenium dimethyl sulfoxide complexes,” Inorg. Chem. 44(22), 8065–8075 (2005). [CrossRef] [PubMed]

Nature

D. Psaltis, S. R. Quake, and C. H. Yang, “Developing optofluidic technology through the fusion of microfluidics and optics,” Nature 442(7101), 381–386 (2006). [CrossRef] [PubMed]

Phys. Chem. Chem. Phys.

D. Schaniel, B. Cormary, I. Malfant, L. Valade, Th. Woike, B. Delley, K. W. Kramer, and H. U. Güdel, “Generation of one light-induced metastable nitrosyl linkage isomer in [Pt(NH3)4Cl(NO)]Cl2 in the red spectral range,” Phys. Chem. Chem. Phys. 9(28), 3717–3724 (2007). [CrossRef] [PubMed]

Phys. Rep.

P. Günter, “Holography, coherent light amplification and optical phase conjugation with photorefractive materials,” Phys. Rep. 93(4), 199–299 (1982). [CrossRef]

Phys. Rev. B

D. Schaniel, Th. Woike, C. Merschjann, and M. Imlau, “Transient kinetics of light-induced metastable states in single crystals and aqueous solutions of Na2[Fe(CN)5NO]∙2H2O,” Phys. Rev. B 72(19), 195119 (2005). [CrossRef]

Other

J. J. Rack, “Photoinduced molecular switches,” U.S. patent 6,433,270 (2002)

2007, Schaniel, Phys. Chem. Chem. Phys.
2007, Schaniel, Adv. Mater.
2006, Butcher, Inorg. Chem.
2006, Psaltis, Nature
2005, Schaniel, Phys. Rev. B
2005, Rachford, Inorg. Chem.
2002, Coppens, Chem. Rev.
2001, Gütlich, Coord. Chem. Rev.
1999, Imlau, Appl. Phys. B
1996, Woike, Appl. Phys. B
1985, Root, Inorg. Chem.
1982, Günter, Phys. Rep.

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