A sustainable four-step synthesis of soluble perylenophanes for applications as fluorescent optical functional materials is presented and even allows upscaling because of starting with technical bulk products. Thus, terminal alkenylnitriles were alkylated reduced to amines, condensed with perylenetetracarboxylic bisanhydride and cyclised to cyclophanes by means of double cross metathesis in yields until 69% of isolated dyes. The first metathesis by means of the second-generation Hoveyda-Grubbs-catalyst brings the remaining reactive olefinic groups close together favouring the ring-closure to the cyclophanes where the locked neighboring of chromophores in a skew arrangement induce strong exciton interactions. The latter cause an increased the Stokes’ separation by means of a moderate hypsochromic shift of light absorption and a stronger bathochromic shift of fluorescence. Various applications such as for lasers, photonics, solar collectors or in analytics are discussed.
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Langhals, H. and Ismael, R. (1998) Cyclophanes as Model Compounds for Permanent, Dynamic Aggregates—Induced Chirality with Strong CD Effects. European Journals of Organic Chemistry, 1998, 1915-1917. https://doi.org/10.1002/(SICI)1099-0690(199809)1998:9 3.0.CO;2-1
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Langhals, H., Demmig, S. and Huber, H. (1988) Rotational Barriers in Perylene Fluorescent Dyes. Spectrochimica Acta A, 44, 1189-1193. https://doi.org/10.1016/0584-8539(88)80091-6
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Langhals, H. and Bastani-Oskoui, H. (1997) Synthesis of Readily Soluble Tetraazaviolanthrone and Isoviolanthrone Fluorescent Dyes. Journal für Praktische Chemie, 339, 597-602. https://doi.org/10.1002/prac.199733901107
Langhals, H., Ismael, R. and Yürük, O. (2000) Persistent Fluorescence of Perylene Dyes by Steric Inhibition of Aggregation. Tetrahedron, 56, 5435-5441. https://doi.org/10.1016/S0040-4020(00)00452-X
Langhals, H. and Rüchardt, C. (1981) Wanderungstendenzen cyclischer, polycyclischer und methylverzweigter Alkylreste bei der Beckmann-Umlagerung. Chemische Berichte, 114, 3831-3854. https://doi.org/10.1002/cber.19811141208
Missling, C.U., Sünkel, K., Langhals, H. and Beck, W. (2017) Organometallic Lewis Acids, Part CXII. Chiral Carbonyl-Cyclopentadienyl-Triphenylphosphine-Iron and -Ruthenium Complexes with Novel Tertiary Nitriles. [CpM(CO)(PPh 3 )(N≡C-CR 1 R 2 R 3 )]+ BF 4 - (M = Fe, Ru). Zeitschrift für anorganische und allgemeine Chemie, 643, 1262-1268. https://doi.org/10.1002/zaac.201700235
Langhals, H. (1985) Synthese von hochreinen Perylen-Fluoreszenzfarbstoffen in groben Mengen-gezielte Darstellung von Atrop-Isomeren. Chemische Berichte, 118, 4641-4645. https://doi.org/10.1002/cber.19851181138
Langhals, H., Demmig, S. and Potrawa, T. (1991) The Relation between Packing Effects and Solid State Fluorescence of Dyes. Journal für Praktishe Chemie, 333, 733-748. https://doi.org/10.1002/prac.19913330508
Langhals, H. and Jona, W. (1998) Intense Dyes through Chromophore-Chromophore Interactions: Bi- and Trichromophoric Perylene-3,4:9,10-bis(dicarboximide)s. Angewandze Chemie International Edition, 37, 952-955. https://doi.org/10.1002/(SICI)1521-3773(19980420)37:7 3.0.CO;2-4
Langhals, H. and Gold, J. (1996) Tangentially Coupled π Systems and Their Through-Space Interaction-Trichromophoric Perylene Dyes. Journal für Praktische Chemie, 338, 654-659. https://doi.org/10.1002/prac.199633801124
Langhals, H. and Pust, T. (2011) Lipophilic Optical Supramolecular Nano Devices in the Aqueous Phase. Green and Sustainable Chemistry, 1, 1-6. https://doi.org/10.4236/gsc.2011.11001
Feng, J., Zhang, Y., Zhao, C., Li, R., Xu, W., Li, X. and Jiang, J. (2008) Cyclophanes of Perylene Tetracarboxylic Diimide with Different Substituents at Bay Positions. Chemistry: An European Journal, 14, 7000-7010. https://doi.org/10.1002/chem.200800136
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Langhals, H. (1981) Prinzipielle Wege für die Gewinnung von Solarenergie über gezielte Modifizierung fluoreszierender Systeme.
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Farrugia, L.J. (2012) WinGX and ORTEP for Windows: An Update. Journal of Applied Crystallography, 45, 849-854. https://doi.org/10.1107/S0021889812029111
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Tsuji, J., Yamada, T., Minami, I., Yuhara, M., Nisar, M. and Shimizu, I. (1987) Palladium-Catalyzed Decarboxylation-Allylation of Allylic Esters of α-Substituted β-Keto Carboxylic, Malonic, Cyanoacetic, and Nitroacetic Acids. Journal of Organic Chemistry, 52, 2988-2995. https://doi.org/10.1021/jo00390a007
Langhals, H., Karolin, J. and Johansson, L.B.-A. (1998) Spectroscopic Properties of New and Convenient Standards for Measuring Fluorescence Quantum Yields. Journal of the Chemical Society, Faraday Transactions, 94, 2919-2922. https://doi.org/10.1039/a804973d