Multistimuli two-color luminescence switching via different slip-stacking of highly fluorescent molecular sheets.

Color tuning and switching of the solid-state luminescence of organic materials are attractive subjects for both the fundamental research and practical applications such as optical recording. We report herein cyanostilbene-based highly luminescent molecular sheets which exhibit two-color fluorescence switching in response to pressure, temperature, and solvent vapor. The origin for the multistimuli luminescence switching is the two-directional shear-sliding capability of molecular sheets, which are formed via intermolecular multiple C-H···N and C-H···O hydrogen bonds. The resulting two distinctive crystal phases are promoted by different modes of local dipole coupling, which cause a substantial alternation of π-π overlap. These changes can be directly correlated with the subsequent intermolecular excitonic and excimeric coupling in both phases, as demonstrated by an in-depth theory-assisted spectroscopic and structural study. Finally, we have prepared a first device demonstrator for rewritable fluorescent optical recording media which showed multistimuli luminescence tuning with fast response. Our multistimuli responsive system is unique in terms of the slip-stacking of molecular sheets and thus provides a novel concept of rewritable fluorescent optical recording media.

[1]  Michael Hanack,et al.  Tuning of Fluorescence in Films and Nanoparticles of Oligophenylenevinylenes , 1998 .

[2]  Yu Liu,et al.  Thermally Induced Reversible Phase Transformations Accompanied by Emission Switching Between Different Colors of Two Aromatic‐Amine Compounds , 2009 .

[3]  I. Gould,et al.  A theoretical and experimental study of cyano- and alkoxy-substituted phenylenevinylene model compounds , 2000 .

[4]  Soo Young Park,et al.  Photoswitchable organic nanoparticles and a polymer film employing multifunctional molecules with enhanced fluorescence emission and bistable photochromism. , 2004, Angewandte Chemie.

[5]  Kenji Matsumoto,et al.  Brilliant reversible luminescent mechanochromism of silver(I) complexes containing o-bis(diphenylphosphino)benzene and phosphinesulfide. , 2010, Chemical communications.

[6]  Ian D. Williams,et al.  Aggregation-induced and crystallization-enhanced emissions of 1,2-diphenyl-3,4-bis(diphenylmethylene)-1-cyclobutene. , 2007, Chemical communications.

[7]  Patrice L. Baldeck,et al.  Polymorphism and luminescence properties of CMONS organic crystals: bulk crystals and nanocrystals confined in gel-glasses , 2001 .

[8]  N. S. S. Kumar,et al.  Solid State Optical Properties of 4-Alkoxy-pyridine Butadiene Derivatives: Reversible Thermal Switching of Luminescence , 2008 .

[9]  Christoph Weder,et al.  Oligo(p‐phenylene vinylene)s as a “New” Class of Piezochromic Fluorophores , 2008 .

[10]  K. Solntsev,et al.  Activation and tuning of green fluorescent protein chromophore emission by alkyl substituent-mediated crystal packing. , 2009, Journal of the American Chemical Society.

[11]  A. Ajayaghosh,et al.  Reversible self-assembly of entrapped fluorescent gelators in polymerized styrene gel matrix: erasable thermal imaging via recreation of supramolecular architectures. , 2009, Journal of the American Chemical Society.

[12]  T. Yamaki,et al.  Novel superstructure of nondiscoid mesogens: uneven-parallel association of half-disk molecules, 3,4,5-trialkoxybenzoic anhydrides, to a columnar structure and its one-directionally geared interdigitation. , 2002, Journal of the American Chemical Society.

[13]  Masahiro Tanaka,et al.  Self-assembly of tris(phenylisoxazolyl)benzene and its asymmetric induction of supramolecular chirality. , 2008, Chemical communications.

[14]  T. Mutai,et al.  Switching of polymorph-dependent ESIPT luminescence of an imidazo[1,2-a]pyridine derivative. , 2008, Angewandte Chemie.

[15]  Takashi Kato,et al.  A Stimuli‐Responsive, Photoluminescent, Anthracene‐Based Liquid Crystal: Emission Color Determined by Thermal and Mechanical Processes , 2009 .

[16]  Jong Won Chung,et al.  A Thermoreversible and Proton-Induced Gel−Sol Phase Transition with Remarkable Fluorescence Variation , 2008 .

[17]  D. Bruce,et al.  Phosphorescent, terdentate, liquid-crystalline complexes of platinum(II): stimulus-dependent emission. , 2008, Angewandte Chemie.

[18]  Takakazu Yamamoto,et al.  New Alternative Donor−Acceptor Arranged Poly(Aryleneethynylene)s and Their Related Compounds Composed of Five-Membered Electron-Accepting 1,3,4-Thiadiazole, 1,2,4-Triazole, or 3,4-Dinitrothiophene Units: Synthesis, Packing Structure, and Optical Properties , 2005 .

[19]  M. Kasha,et al.  The exciton model in molecular spectroscopy , 1965 .

[20]  Soon-Ki Kwon,et al.  Highly Sensitive Fluorescence Probes for Organic Vapors: On/off and Dual Color Fluorescence Switching , 2005 .

[21]  Ian D. Williams,et al.  Switching the light emission of (4-biphenylyl)phenyldibenzofulvene by morphological modulation: crystallization-induced emission enhancement. , 2007, Chemical communications.

[22]  C. Suresh,et al.  Correlation between Solid-State Photophysical Properties and Molecular Packing in a Series of Indane-1,3-dione Containing Butadiene Derivatives† , 2009 .

[23]  Soon-Ki Kwon,et al.  Color-tuned highly fluorescent organic nanowires/nanofabrics: easy massive fabrication and molecular structural origin. , 2009, Journal of the American Chemical Society.

[24]  J. Gierschner,et al.  Highly luminescent oligo(phenylenevinylene) films: the stereochemical approach , 2001 .

[25]  G. Viscardi,et al.  4- Tert-butyl-1-(4'-dimethylamino-benzylideneamino)pyridinium perchlorate (BDPP): a novel fluorescent dye , 1993 .

[26]  Seong-Jun Yoon,et al.  Dual-mode switching in highly fluorescent organogels: binary logic gates with optical/thermal inputs. , 2009, Angewandte Chemie.

[27]  J. Gierschner,et al.  Luminescence of conjugated molecules confined in nanochannels , 2003 .

[28]  J. Gierschner,et al.  Modeling of the optical properties of cofacial chromophore pairs: Stilbenophane , 2004 .

[29]  R. Friend,et al.  Excitonic versus electronic couplings in molecular assemblies: The importance of non-nearest neighbor interactions. , 2009, The Journal of chemical physics.

[30]  F. Würthner,et al.  Transformation from H- to J-aggregated perylene bisimide dyes by complexation with cyanurates. , 2008, Angewandte Chemie.

[31]  Y. Wang,et al.  Organic Crystals with Tunable Emission Colors Based on a Single Organic Molecule and Different Molecular Packing Structures , 2006 .

[32]  Guoqing Zhang,et al.  Mechanochromic luminescence quenching: force-enhanced singlet-to-triplet intersystem crossing for iodide-substituted difluoroboron-dibenzoylmethane-dodecane in the solid state. , 2010, Inorganic chemistry.

[33]  Takashi Kato,et al.  Stimuli-responsive luminescent liquid crystals: change of photoluminescent colors triggered by a shear-induced phase transition. , 2008, Angewandte Chemie.

[34]  E. W. Meijer,et al.  About Supramolecular Assemblies of π-Conjugated Systems , 2005 .

[35]  I. Cacelli,et al.  Theoretical study of building blocks for molecular switches based on electrically induced conformational changes , 2006 .

[36]  Jong Won Chung,et al.  Shear- and UV-induced fluorescence switching in stilbenic pi-dimer crystals powered by reversible [2 + 2] cycloaddition. , 2009, Journal of the American Chemical Society.

[37]  Sang-Don Jung,et al.  Enhanced emission and its switching in fluorescent organic nanoparticles. , 2002, Journal of the American Chemical Society.

[38]  I. Javed,et al.  Anthracene-Arrangement-Dependent Emissions of Crystals of 9-Anthrylpyrazole Derivatives , 2009 .

[39]  G. U. Kulkarni,et al.  The influence of crystal packing on the solid state fluorescence behavior of alkyloxy substituted phenyleneethynylenes , 2009 .

[40]  Jie Cao,et al.  Solid-state packing of conjugated oligomers: from pi-stacks to the herringbone structure. , 2004, Journal of the American Chemical Society.

[41]  C. Suresh,et al.  Molecular Packing and Solid-State Fluorescence of Alkoxy-Cyano Substituted Diphenylbutadienes: Structure of the Luminescent Aggregates , 2008 .

[42]  Guoqing Zhang,et al.  Polymorphism and reversible mechanochromic luminescence for solid-state difluoroboron avobenzone. , 2010, Journal of the American Chemical Society.

[43]  Yukio Hinatsu,et al.  Reversible mechanochromic luminescence of [(C6F5Au)2(mu-1,4-diisocyanobenzene)]. , 2008, Journal of the American Chemical Society.

[44]  David Beljonne,et al.  Solid-state optical properties of linear polyconjugated molecules: pi-stack contra herringbone. , 2005, The Journal of chemical physics.

[45]  Takuzo Aida,et al.  Rewritable phosphorescent paper by the control of competing kinetic and thermodynamic self-assembling events , 2005, Nature materials.

[46]  J. Rieger,et al.  Organic Nanoparticles in the Aqueous Phase-Theory, Experiment, and Use. , 2001, Angewandte Chemie.

[47]  Michele Muccini,et al.  Correlation between Molecular Packing and Optical Properties in Different Crystalline Polymorphs and Amorphous Thin Films of mer-Tris(8-hydroxyquinoline)aluminum(III) , 2000 .

[48]  E. W. Meijer,et al.  Highly fluorescent crystalline and liquid crystalline columnar phases of pyrene-based structures. , 2006, The journal of physical chemistry. B.

[49]  Soo Young Park,et al.  Strongly fluorescent organogel system comprising fibrillar self-assembly of a trifluoromethyl-based cyanostilbene derivative. , 2004, Journal of the American Chemical Society.

[50]  Hirohiko Houjou,et al.  Fluorescence Color Modulation by Intramolecular and Intermolecular π−π Interactions in a Helical Zinc(II) Complex , 2005 .

[51]  N. Rath,et al.  Thermally reversible fluorescent polymorphs of alkoxy-cyano-substituted diphenylbutadienes: role of crystal packing in solid state fluorescence. , 2004, Chemical communications.

[52]  M. Hanack,et al.  Structural influences on luminescence properties of substituted ppvs and model compounds , 1999 .

[53]  U. Stalmach,et al.  Towards highly luminescent phenylene vinylene films , 1996 .

[54]  Soon-Ki Kwon,et al.  Photopatterned arrays of fluorescent organic nanoparticles. , 2007, Angewandte Chemie.

[55]  G. Hadziioannou,et al.  Synthesis and Crystal Structure of a Cyano-Substituted Oligo(p-phenylenevinylene) , 1996 .

[56]  Soo Young Park,et al.  Bistable Photoswitching in the Film of Fluorescent Photochromic Polymer: Enhanced Fluorescence Emission and Its High Contrast Switching , 2005 .

[57]  Takashi Kato,et al.  Mechanically induced luminescence changes in molecular assemblies. , 2009, Nature chemistry.

[58]  Hiroyuki Satou,et al.  Reproducible on–off switching of solid-state luminescence by controlling molecular packing through heat-mode interconversion , 2005, Nature materials.

[59]  T. Mutai,et al.  Material design for piezochromic luminescence: hydrogen-bond-directed assemblies of a pyrene derivative. , 2007, Journal of the American Chemical Society.