Linear and Nonlinear Optical Molecular Switches Based on Photochromic Metal Complexes

  • Véronique Guerchais
  • Julien Boixel
  • Hubert Le Bozec


This chapter is devoted to our works made in the area of photochromic organometallic compounds which can be used for the photomodulation of the quadratic nonlinear optical (NLO) properties and for the photoregulation of the emission properties of the resulting systems. The first part is related to the design of chromophores combining two types of dithienylethene (DTE)-based bipyridine ligands with different metal fragments (ReI, FeII, RuII, IrIII, CuI, ZnII) which give rise to multi-photochromic metal complexes. The photoregulation of their quadratic nonlinear optical (NLO) properties, as well as their luminescence properties, is then discussed. The last part deals with the synthesis, photochromic properties, and NLO-switching behavior of Cyclometallated platinum (II) complexes containing two types of DTE units bound to the metal through an alkynyl linkage.


Photochromes Metal complexes Bipyridines Alkynyl ligands Nonlinear optics Luminescence 



We are grateful to the very talented graduate students and colleagues for their outstanding contributions; their names are given in the references. This work has been financially supported by ANR (BLANC COMET), LEA Rennes-Durham (Molecular Materials and Catalysis) and the Région Bretagne.


  1. 1.
    Coe BJ (1999) Molecular materials possessing switchable quadratic nonlinear optical properties. Chem Eur J 5:2464–2471CrossRefGoogle Scholar
  2. 2.
    Delaire JA, Nakatani K (2000) Linear and nonlinear optical properties of photochromic molecules and materials. Chem Rev 100:1817–1845CrossRefGoogle Scholar
  3. 3.
    Gilat SL, Kawai SH, Lehn JM (1995) Light-triggered molecular devices: photochemical switching of optical and electrochemical properties in molecular wire type diarylethene species. Chem Eur J 1:275–284CrossRefGoogle Scholar
  4. 4.
    Nakatani K, Delaire JA (1997) Reversible photoswitching of second-order nonlinear optical properties in an organic photochromic crystal. Chem Mater 9:2682–2684CrossRefGoogle Scholar
  5. 5.
    Giraud M, Léaustic A, Guillot R, Yu P, Lacroix PG, Nakatani K, Pansu R, Maurel F (2007) Dithiazolylethene-based molecular switches for nonlinear optical properties and fluorescence: synthesis, crystal structure and ligating properties. J Mater Chem 17:4414–4425CrossRefGoogle Scholar
  6. 6.
    Mançois F, Pozzo JL, Pan J, Adamietz F, Rodriguez V, Ducasse L, Castet F, Plaquet A, Champagne B (2009) Two-way molecular switches with large nonlinear optical contrast. Chem Eur J 15:2560–2571CrossRefGoogle Scholar
  7. 7.
    Irie M (2000) Diarylethenes for memories and switches. Chem Rev 100:1685–1716CrossRefGoogle Scholar
  8. 8.
    Irie M, Fukaminato T, Matsuda K, Kobatake S (2014) Photochromism of diarylethene molecules and crystals: memories, switches, and actuators. Chem Rev 114:12174–12277CrossRefGoogle Scholar
  9. 9.
    Sénéchal K, Maury O, Le Bozec H, Ledoux I, Zyss J (2002) Zinc(II) as a versatile template for the design of dipolar and octupolar NLO-phores. J Am Chem Soc 124:4561–4562CrossRefGoogle Scholar
  10. 10.
    Maury O, Le Bozec H (2005) Molecular engineering of octupolar NLO molecules and materials based on bipyridyl metal complexes. Acc Chem Res 38:691–704CrossRefGoogle Scholar
  11. 11.
    Bourgault M, Baum K, Le Bozec H, Ledoux I, Pucetti G, Zyss J (1998) Synthesis and molecular hyperpolarisabilities of donor-acceptor bipyridyl metal complexes (M = Re, Hg, Zn). New J Chem 517–522Google Scholar
  12. 12.
    Baccouche A, Peigné B, Ibersiene F, Hammoutène D, Boutarfaïa A, Boucekkine A, Feuvrie C, Maury O, Ledoux I, Le Bozec H (2010) Effects of the metal center and substituting groups on the linear and nonlinear optical properties of substituted styryl-bipyridine metal(II) dichloride complexes: DFT and TDDFT computational investigations and harmonic light scattering measurements. J Phys Chem A 114:5429–5438CrossRefGoogle Scholar
  13. 13.
    Le Bouder T, Maury O, Le Bozec H, Ledoux I, Zyss J (2001) Design and synthesis of a highly thermally stable octupolar polyimide for nonlinear optics. Chem Comm 2430–2431Google Scholar
  14. 14.
    Le Bouder T, Maury O, Le Bozec H, Bondon A, Costuas K, Amouyal E, Zyss J, Ledoux I (2003) Synthesis, photophysical and nonlinear optical properties of macromolecular architectures featuring octupolar tris(bipyridine) ruthenium(II) moieties: evidence for a supramolecular self-ordering in a dentritic structure. J Am Chem Soc 125:12884–12899CrossRefGoogle Scholar
  15. 15.
    Maury O, Viau L, Sénéchal K, Corre B, Guégan JP, Renouard T, Ledoux I, Zyss J, Le Bozec H (2004) Synthesis, linear and quadratic nonlinear optical properties of octupolar D3 and D2d bipyridyl metal complexes. Chem Eur J 10:4454–4466CrossRefGoogle Scholar
  16. 16.
    Renouard T, Le Bozec H, Brasselet S, Ledoux I, Zyss J (1999) Tetrahedral bipyridyl copper(I) complexes: a new class of non dipolar chromophores nonlinear optics. Chem Commun 871–872Google Scholar
  17. 17.
    Yin B, Niemeyer F, Williams JAG, Jiang J, Boucekkine A, Toupet L, Le Bozec H, Guerchais V (2006) Synthesis, structure and photophysical properties of luminescent platinum(II) complexes containing cyclometallated 4-styryl-functionalized 2-phenylpyridine ligands. Inorg Chem 45:8584–8596Google Scholar
  18. 18.
    Colombo A, Dragonetti C, Marinotto D, Righetto S, Roberto D, Tavazzi S, Escadeillas M, Guerchais V, Le Bozec H, Bouccekine A, Latouche C (2013) Cyclometallated 4-styryl-2-phenylpyridine Pt(II) acetylacetonate complexes as second-order NLO building blocks for SHG active polymeric films. Organometallics 32:3890–3894Google Scholar
  19. 19.
    Lanoë PH, Fillaut JL, Toupet L, Williams JAG, Le Bozec H, Guerchais V (2008) Cyclometallated platinum(II) complexes incorporating ethynyl-flavone ligands: switching between triplet and singlet emission induced by selective binding of Pb2+ ions. Chem Commun 4333–4335Google Scholar
  20. 20.
    Aubert V, Guerchais V, Ishow E, Hoang-Thi K, Ledoux I, Nakatani K, Le Bozec H (2008) Efficient photoswitching of the nonlinear optical properties of dipolar photochromic zinc(II) complexes. Angew Chem Int Ed 47:577–580CrossRefGoogle Scholar
  21. 21.
    Ordronneau L, Nitadori H, Ledoux I, Singh A, Williams JAG, Akita M, Guerchais V, Le Bozec H (2012) Photochromic metal complexes: photoregulation of both the nonlinear optical and luminescent properties. Inorg Chem 51:5627–5636CrossRefGoogle Scholar
  22. 22.
    Ordronneau L, Aubert V, Métivier R, Ishow E, Boixel J, Nakatani K, Ibersiene F, Hammoutène D, Boucekkine A, Le Bozec H, Guerchais V (2012) Tunable double photochromism of a family of Bis-DTE bipyridine ligands and their dipolar Zn complexes. Phys Chem Chem Phys 14:2599–2605CrossRefGoogle Scholar
  23. 23.
    Aubert V, Ishow E, Guerchais V, Le Bozec H, Ibersiene F, Boucekkine A, Toupet L, Métivier R, Williams JAG (2009) A reverse interruptor: novel molecular design of a fluorescent photochromic DTE-based bipyridine. New J Chem 33:1320–1323CrossRefGoogle Scholar
  24. 24.
    Ordronneau L, Boixel J, Aubert V, Vidal MS, Moya S, Aguirre P, Toupet L, Williams JAG, Le Bozec H, Guerchais V (2014) New fluorescent bis dithienylethene (DTE)-based bipyridines as reverse interrupters: single vs double photochromism. Org Biomol Chem 12:979–992CrossRefGoogle Scholar
  25. 25.
    Aubert V, Ordronneau L, Escadeillas M, Williams JAG, Boucekkine A, Coulaud E, Dragonetti C, Righetto S, Roberto D, Ugo R, Valore A, Singh A, Ledoux-Rak I, Zyss J, Le Bozec H, Guerchais V (2011) Linear and nonlinear optical properties of cationic iridium(III) complexes: tunable and photoswitchable? Inorg Chem 50:5027–5038CrossRefGoogle Scholar
  26. 26.
    Coe BJ, Harris JA, Brunschwig BS, Asselberghs I, Clays K, Garın J, Orduna J (2005) Three-dimensional nonlinear optical chromophores based on metal-to-ligand charge-transfer from ruthenium(II) or iron(II) centers. J Am Chem Soc 127:13399–13410CrossRefGoogle Scholar
  27. 27.
    Yumoto K, Irie M, Matsuda K (2008) Control of the photoreactivity of diarylethene derivatives by quaternarization of the pyridylethynyl group. Org Lett 10:2051–2054CrossRefGoogle Scholar
  28. 28.
    Nitadori H, Ordronneau L, Boixel J, Jacquemin D, Boucekkine A, Singh A, Akita M, Ledoux I, Guerchais V, Le Bozec H (2012) Photoswitching of the second-order nonlinearity of a tetrahedral octupolar multi DTE-based copper(I) complex. Chem Commun 48:10395–10397CrossRefGoogle Scholar
  29. 29.
    Ordronneau L, Aubert V, Guerchais V, Boucekkine A, Le Bozec H, Singh A, Ledoux I, Jacquemin D (2013) The first hexa DTE-based metal complexes as quadratic NLO photoswitches: combined experimental and DFT studies. Chem Eur J 19:5845–5848CrossRefGoogle Scholar
  30. 30.
    For a recent review, see: Williams JAG, Develay S, Rochester DL, Murphy L (2008) Optimising the luminescence of platinum(II) complexes and their application in organic light emitting devices (OLEDs). Coord Chem Rev 252:2596–2611Google Scholar
  31. 31.
    Roberts MN, Carling CJ, Nagle JK, Branda NR, Wolf MO (2009) Successful bifunctional photoswitching and electronic communication of two platinum(II) acetylide bridged dithienylethenes. J Am Chem Soc 131:16644–16645Google Scholar
  32. 32.
    Roberts MN, Nagle JK, Majewski MB, Finden N, Branda GR, Wolf MO (2011) Charge transfer and intraligand excited state interactions in platinum-sensitized dithienylethenes. Inorg Chem 50:4956–4966CrossRefGoogle Scholar
  33. 33.
    Chan JCH, Lam WH, Wong HL, Zhu N, Wong WT, Yam VWW (2011) Diarylethene-containing cyclometalated platinum(II) complexes: tunable photochromism via metal coordination and rational ligand design. J Am Chem Soc 133:12690–12705CrossRefGoogle Scholar
  34. 34.
    Brayshaw SK, Schiffers S, Stevenson AJ, Teat SJ, Warren MR, Bennett RD, Sazanovich IV, Buckley AR, Weinstein JA, Raithby PR (2011) Highly efficient visible-light driven photochromism: developments towards a solid-state molecular switch operating through a triplet-sensitised pathway. Chem Eur J 17:4385–4395CrossRefGoogle Scholar
  35. 35.
    Zhang MY, Wang CH, Wang WY, Ma NN, Sun SL, Qiu YQ (2013) Strategy for enhancing second-order nonlinear optical properties of the Pt(II) dithienylethene complexes: substituent effect, π-conjugated influence, and photoisomerization switch. J Phys Chem A 117:12497–12510CrossRefGoogle Scholar
  36. 36.
    Boixel J, Guerchais V, Le Bozec H, Jacquemin D, Amar A, Boucekkine A, Colombo A, Dragonetti C, Marinotto D, Roberto D, Righetto S, De Angelis R (2014) Second-order NLO switches from molecules to polymer films based on photochromic cyclometalated platinum(II) complexes. J Am Chem Soc 136:5367–5375CrossRefGoogle Scholar
  37. 37.
    Boixel J, Guerchais V, Le Bozec H, Chantzis A, Jacquemin D, Colombo A, Dragonetti C, Righetto S, Roberto D (2015) Sequential double second-order nonlinear optical switch by an acido-triggered photochromic cyclometallated platinum(II) complex. Chem Comm 51:7805–7808CrossRefGoogle Scholar
  38. 38.
    Lu W, Mi BX, Chan MCW, Hui Z, Che CM, Zhu N, Lee ST (2004) Light-emitting tridentate cyclometalated platinum(II) complexes containing σ-alkynyl auxiliaries: tuning of photo- and electrophosphorescence. J Am Chem Soc 126:4958–4971CrossRefGoogle Scholar

Copyright information

© Springer Japan KK 2017

Authors and Affiliations

  • Véronique Guerchais
    • 1
  • Julien Boixel
    • 1
  • Hubert Le Bozec
    • 1
  1. 1.Institut des Sciences Chimiques de RennesUMR 6226 CNRS-Université de Rennes1, Campus de BeaulieuRennes CedexFrance

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