Fluorescent J-type aggregates and thermotropic columnar mesophases of perylene bisimide dyes.

A series of perylene tetracarboxylic acid bisimides 3a-e bearing 3,4,5-tridodecyloxyphenyl substituents on the imide N atoms and zero, two, or four phenoxy-type substituents in the bay positions of the perylene core were synthesized. From investigations of their spectroscopic properties and aggregation behavior in low-polarity solvents by absorption and fluorescence optical spectroscopy, not only were these compounds found to form fluorescent J-type aggregates, but also binding constants for aggregation could be derived which reflect the number and steric demand of the phenoxy substituents for bisimides 3a-d. In the pristine state, 3a-d form thermotropic hexagonal columnar mesophases which exist over a broad temperature range from below -30 degrees C to over 300 degrees C. For the tetraphenoxy-substituted compound 3e, however, a layered crystalline structure was found. This difference in behavior can be explained by the concept of microphase segregation of the aromatic cores of the molecules and the alkyl chains at the periphery. The high stability and bright fluorescence of the mesophase of several of the compounds make them promising for applications as polarizers or components in (opto)electronic devices.

[1]  F. Würthner,et al.  Hierarchical Self‐Organization of Perylene Bisimide–Melamine Assemblies to Fluorescent Mesoscopic Superstructures , 2000 .

[2]  J. G. Vinter,et al.  Complimentary Polytopic Interactions , 2000 .

[3]  C. Böttcher,et al.  Supramolecular Structures of J-Aggregates of Carbocyanine Dyes in Solution , 2000 .

[4]  Frank Würthner,et al.  Substituierte Diazadibenzoperylene: neue Funktionsbausteine für die supramolekulare Chemie , 2000 .

[5]  Sautter,et al.  Substituted Diazadibenzoperylenes: New Functional Building Blocks for Supramolecular Chemistry This work was supported by the Ulmer Universitätsgesellschaft, the Fonds der Chemischen Industrie (Liebig grant for F. W.), and the Deutsche Forschungsgemeinschaft (Habilitandenstipendium for F. W.). We ar , 2000, Angewandte Chemie.

[6]  D. Schlettwein,et al.  Suppression of chromophore coupling in thin films by chemical substitution of a perylene tetracarboxylic acid diimide , 2000 .

[7]  K. Müllen,et al.  Hybrid Materials Doped with Covalently Bound Perylene Dyes through the Sol-Gel Process , 2000 .

[8]  J. Wendorff,et al.  Diskotische Flüssigkristalle: Materialien für die Optoelektronik , 2000 .

[9]  F. Würthner,et al.  Highly fluorescent and electroactive molecular squares containing perylene bisimide ligands , 2000 .

[10]  H. Eichhorn.  Mesomorphic phthalocyanines, tetraazaporphyrins, porphyrins and triphenylenes as charge‐transporting materials , 2000 .

[11]  S. Tam-Chang,et al.  Cascade of Molecular Order by Sequential Self-Organization, Induced Orientation, and Order Transfer Processes , 1999 .

[12]  F. Würthner,et al.  Hierarchical Organization of Functional Perylene Chromophores to Mesoscopic Superstructures by Hydrogen Bonding and π–π Interactions , 1999 .

[13]  S. Diele,et al.  The Importance of Micro Segregation for Mesophase Formation: Thermotropic Columnar Mesophases of Tetrahedral and other Low‐Aspect‐Ratio Organic Materials , 1999 .

[14]  J. Meyer,et al.  Molecular Interactions in Thin Films of Hexadecafluorophthalocyaninatozinc (F16PcZn) as Compared to Islands of N,N‘-Dimethylperylene-3,4,9,10-biscarboximide (MePTCDI) , 1999 .

[15]  Andreas Herrmann,et al.  Electrochemistry, Spectroscopy and Electrogenerated Chemiluminescence of Perylene, Terrylene, and Quaterrylene Diimides in Aprotic Solution , 1999 .

[16]  C. Ahn,et al.  Coassembly of a Hexagonal Columnar Liquid Crystalline Superlattice from Polymer(s) Coated with a Three‐Cylindrical Bundle Supramolecular Dendrimer , 1999 .

[17]  B. Gregg,et al.  Liquid Crystal Perylene Diimide Films Characterized by Electrochemical, Spectroelectrochemical, and Conductivity versus Potential Measurements , 1998 .

[18]  H. Langhals,et al.  Cyclophanes as Model Compounds for Permanent, Dynamic Aggregates – Induced Chirality with Strong CD Effects , 1998 .

[19]  C. Bräuchle,et al.  Liquid Crystalline Coronene Derivatives with Extraordinary Fluorescence Properties. , 1998, Angewandte Chemie.

[20]  Klaus Müllen,et al.  Flüssigkristalline Coronenderivate mit außergewöhnlichen Fluoreszenzeigenschaften , 1998 .

[21]  B. Gregg,et al.  Synthesis and Characterization of Liquid Crystalline Perylene Diimides , 1998 .

[22]  B. Gregg,et al.  Self-Organization in Thin Films of Liquid Crystalline Perylene Diimides , 1997 .

[23]  Stephen R. Forrest,et al.  Ultrathin Organic Films Grown by Organic Molecular Beam Deposition and Related Techniques. , 1997, Chemical reviews.

[24]  B. Gregg,et al.  Long-Range Singlet Energy Transfer in Perylene Bis(phenethylimide) Films , 1997 .

[25]  A. Greiner,et al.  Multicoloured chromophore for white‐light‐emitting diodes , 1997 .

[26]  V. Tsukruk,et al.  Columnar discotics for light emitting diodes , 1997 .

[27]  H. Nalwa.  Handbook of organic conductive molecules and polymers , 1997 .

[28]  R. B. Martin,et al.  Comparisons of Indefinite Self-Association Models. , 1996, Chemical reviews.

[29]  K. Müllen,et al.  Novel perylene-containing polymers , 1996 .

[30]  J. Simmerer,et al.  Transient photoconductivity in a discotic hexagonal plastic crystal , 1996 .

[31]  Stephen R. Forrest,et al.  Study of localized and extended excitons in 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) I. Spectroscopic properties of thin films and solutions , 1996 .

[32]  Gilles Horowitz,et al.  Evidence for n‐type conduction in a perylene tetracarboxylic diimide derivative , 1996 .

[33]  W. Harrison,et al.  Liquid-Crystalline J-Aggregates Formed by Aqueous Ionic Cyanine Dyes , 1996 .

[34]  M. Ameloot,et al.  Steady-state and time-resolved fluorescence anisotropy of 2,9-di-n-pentyl-5,6,11,12-tetraazo-5,6,11,12-tetrahydrocoronene-5,6,11,1 2-tetracarboxy-bis-n-heptadecylimide , 1996 .

[35]  C. Tschierske,et al.  Design of non-anisometric and non-amphiphilic liquid crystals: liquid-crystalline tetrahedra , 1996 .

[36]  F. Stöckel,et al.  Anisotropic Structures in Aqueous Solutions of Aggregated Pseudoisocyanine Dyes , 1996 .

[37]  N. J. Baxter,et al.  Stacking interactions between caffeine and methyl gallate , 1996 .

[38]  Heinz Langhals,et al.  Cyclic Carboxylic Imide Structures as Structure Elements of High Stability. Novel Developments in Perylene Dye Chemistry , 1995 .

[39]  Roald Hoffmann,et al.  A THEORETICAL STUDY OF CRYSTALLOCHROMY. QUANTUM INTERFERENCE EFFECTS IN THE SPECTRA OF PERYLENE PIGMENTS , 1994 .

[40]  P. Schuhmacher,et al.  Fast photoconduction in the highly ordered columnar phase of a discotic liquid crystal , 1994, Nature.

[41]  K. Müllen,et al.  SOLUBLE POLYIMIDES CONTAINING PERYLENE UNITS , 1994 .

[42]  K. Müllen,et al.  Liquid‐Crystalline Perylene Derivatives as “Discotic Pigments” , 1993 .

[43]  Klaus Müllen,et al.  Flüssigkristalline Perylenderivate als „discotische Pigmente”† , 1993 .

[44]  C. Hunter.  Arene—Arene Interactions: Electrostatic or Charge Transfer? , 1993 .

[45]  Christopher A. Hunter.  Wechselwirkungen zwischen aromatischen Systemen: Beruhen sie auf elektrostatischen Kräften oder Charge‐Transfer‐Übergängen? , 1993 .

[46]  R. Reisfeld,et al.  Spectroscopy and laser action of the “red perylimide dye” in various solvents , 1993 .

[47]  H. Strzelecka,et al.  Efficient Synthesis of Long‐Chain Substituted Vinamidinium Salts: Positive Salt Effect. , 1993 .

[48]  Kock Yee. Law,et al.  Organic photoconductive materials: recent trends and developments , 1993 .

[49]  P. Bohn.  Aspects of Structure and Energy Transport in Artificial Molecular Assemblies , 1993 .

[50]  H. Löhmannsröben,et al.  A perylene dye in sol—gel matrices: photophysical properties of N,N′-bis(2,5-di-tert-butylphenyl)-3,4:9,10-perylenebis(dicarboximide) in glasses and thin films , 1992 .

[51]  Dieter Meissner,et al.  Organic Solar Cells , 1991 .

[52]  H. Langhals,et al.  The Relation between Packing Effects and Solid State Fluorescence of Dyes , 1991 .

[53]  Christopher A. Hunter,et al.  The nature of .pi.-.pi. interactions , 1990 .

[54]  W. E. Ford,et al.  Photochemistry of 3,4,9,10-perylenetetracarboxylic dianhydride dyes. 4. Spectroscopic and redox properties of oxidized and reduced forms of the bis(2,5-di-tert-butylphenyl)imide derivative , 1989 .

[55]  G. Klebe,et al.  Crystallochromy as a solid-state effect: correlation of molecular conformation, crystal packing and colour in perylene-3,4:9,10-bis(dicarboximide) pigments , 1989 .

[56]  G. Wagenblast,et al.  New perylene and violanthrone dyestuffs for fluorescent collectors , 1989 .

[57]  H. Huber,et al.  Rotational barriers in perylene fluorescent dyes , 1988 .

[58]  Prashant V. Kamat,et al.  Photochemistry of 3,4,9,10-perylenetetracarboxylic dianhydride dyes. 3. Singlet and triplet excited-state properties of the bis(2,5-di-tert-butylphenyl)imide derivative , 1987 .

[59]  George R. Bird,et al.  Improved p-n heterojunction solar cells employing thin film organic semiconductors , 1986 .

[60]  E. Hädicke,et al.  Structures of eleven perylene-3,4:9,10-bis(dicarboximide) pigments , 1986 .

[61]  J. Lakowicz.  Principles of fluorescence spectroscopy , 1983 .

[62]  E. Hädicke,et al.  Kristallstruktur und Farbe bei Perylen‐3,4:9,10‐bis(dicarboximid)‐Pigmenten , 1980 .

[63]  H. Försterling,et al.  Light absorption and structure of aggregates of dye molecules , 1970 .

[64]  G. Bird,et al.  The geometrical structure and absorption spectrum of a cyanine dye aggregate , 1967 .

[65]  D. D. Perrin,et al.  Purification of Laboratory Chemicals , 2022 .

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

[67]  EDWIN E. JELLEY,et al.  Spectral Absorption and Fluorescence of Dyes in the Molecular State , 1936, Nature.