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 Q 0 = (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.

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  1. P. Gütlich, Y. Garcia, and Th. Woike, “Photoswitchable coordination compounds,” Coord. Chem. Rev. 219, 839–879 (2001).
    [CrossRef]
  2. 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]
  3. 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).
  4. 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]
  5. J. J. Rack, “Photoinduced molecular switches,” U.S. patent 6,433,270 (2002)
  6. 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]
  7. 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]
  8. 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]
  9. 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]
  10. 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]
  11. 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]
  12. 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]
  13. P. Günter, “Holography, coherent light amplification and optical phase conjugation with photorefractive materials,” Phys. Rep. 93(4), 199–299 (1982).
    [CrossRef]
  14. 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]

2007 (2)

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]

2006 (2)

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]

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]

2005 (2)

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]

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]

2002 (1)

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]

2001 (1)

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

1999 (1)

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]

1996 (1)

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).

1985 (1)

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]

1982 (1)

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

Angelov, V.

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]

Beckers, J.

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).

Butcher, D. P.

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]

Coppens, P.

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]

Cormary, B.

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]

Delley, B.

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]

Deutsch, E.

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]

Garcia, Y.

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

Güdel, H. U.

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. 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]

Günter, P.

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

Gütlich, P.

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

Haussühl, S.

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]

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).

Imlau, M.

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. 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]

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]

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).

Kovalevsky, A.

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]

Kramer, K. W.

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]

Lutterman, D. A.

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]

Malfant, I.

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]

McClure, B. A.

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]

Merschjann, C.

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]

Mockus, N. V.

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]

Novozhilova, I.

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]

Petersen, J. L.

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]

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]

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]

Psaltis, D.

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]

Quake, S. R.

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]

Rachford, A. A.

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]

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]

Rack, J. J.

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]

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]

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]

Root, M. J.

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]

Rupp, R. A.

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]

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).

Schaniel, D.

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. 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]

Schieder, R.

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]

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).

Schwarz, K.

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]

Sugg, 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).

Turro, C.

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]

Valade, L.

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]

Weisemoeller, T.

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]

Woike, Th.

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. 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, 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]

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

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]

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).

Yang, C. H.

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]

Adv. Mater. (1)

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 (2)

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. (1)

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. (1)

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

Inorg. Chem. (4)

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]

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[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]

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[CrossRef]

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Figures (7)

Fig. 1
Fig. 1

Absorption spectra of a solution of [Ru(bpy)2(OSO)] ∙ PF6 in propylene carbonate (c = 0.20 mmol l−1): Unexposed sample (ground state, black), after an exposure of Q = 1.4 Ws cm−2 at 405 nm (metastable states, blue), and after subsequent relaxation of 20 minutes at room temperature (red).

Fig. 2
Fig. 2

(a) Ground state absorption spectra (GS) fitted with seven Gaussian shaped absorption bands (light gray) and the sum of the fitted bands (dashed red). (b) Absorption spectra of metastable states (MS) with fitted absorption bands and its sum.

Fig. 3
Fig. 3

Relative absorption change Δα as a function of exposure Q (open circles). An exponential fit is depicted as solid line. Pumping wavelength is λ = 405 nm and probing wavelength λ probe = 532 nm (c = 0.88 mmol l−1).

Fig. 4
Fig. 4

Absorption change at 532 nm and 64 °C during the thermal decay (gray circles) on a logarithmic y-axis. Two different decay constants (τ 1, τ 2) can be derived from the data points (black lines). On long time scales a non exponential decay process dominates (light gray circles). Insert: Linear y-axis of the thermal decay of the absorption change.

Fig. 5
Fig. 5

Logarithmic decay constants τ 1 (squares) and τ 2 (dots) versus inverse temperature. Up to 90°C the decay constants follow Arrhenius law (solid lines) yielding E A,1 = (0.76 ± 0.08) eV, E A,2 = (1.00 ± 0.14) eV, and Z 1 = (3.68 ± 0.85) × 109 s−1, Z 2 = (1.79 ± 0.61) × 1012 s−1.

Fig. 6
Fig. 6

Molecular structures of O-bonded metastable states MS1 and MS2 as calculated from DFT [11].

Fig. 7
Fig. 7

Energy level diagram as proposed in Ref [11]. including energy barriers (E A,1 = (0.76 ± 0.08) eV, E A,2 = (1.00 ± 0.14) eV) for the thermal decay from MS1,2 to GS.

Equations (3)

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Δα(Q)=α(Q)α(Q=0)=1dln(I(Q)I0)
τ=1Zexp(EAkBT)
S(λ)=Δα(λ)Q0c

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