Molekulares Design von neuen lumineszierenden Komplexen basierend auf Hybridphosphanliganden für Anwendungen als Chemo- und Biosensoren
Zusammenfassung der Projektergebnisse
Luminescent metal complexes have attracted increasing attention over the last few decades for widespread applications, such as in photochemistry, organic optoelectronics, and in the development of luminescent sensors. In contrast to organic fluorophores, which are singlet emitters, transition metal complexes display triplet emission due to spin–orbit coupling, which leads to efficient singlet–triplet state mixing and enhancement of phosphorescence. The properties of the excited states depend on the metal centre and the ligands, and thus, the photophysical properties (such as emission wavelength, lifetime, and intensity) can be modified for specific applications. This joint project aimed to provide access to novel luminescent systems based on the class of multidonor hybrid phosphorus-containing heterocycles, namely cyclic aminomethylphosphines, and their transition metal complexes with AuI, CuI, and PtII for applications in biosensing and bioimaging. Cyclic aminomethylphosphines are of interest because they are not only structure-forming ligands, but can also be functionalised easily with luminescent and sensing moieties with retention of the coordinating framework. A library of 1,5-diaza-3,7-diphosphacyclooctane ligands with different physical and stereoelectronic properties has been synthesised by condensation reaction of primary heteroaryl phosphines with formaldehyde and subsequent ring formation through addition of primary amines. Chromophoric heteroaromatic substituents at phosphorus and nitrogen provide luminescence properties and additional binding sites for heterometallic assemblies. A wide range of mono- and dinuclear complexes of copper(I), gold(I) and platinum(II) with 1,5- diaza-3,7-diphosphacyclooctane ligands containing heteroaryl substituents at phosphorus and aryl or alkylaryl substituents at nitrogen were obtained and fully characterised in solution and the solid state. Cationic complexes of copper(I) and dinuclear complexes of gold(I) proved to be the most promising candidates in terms of creating sensors capable of responding to external factors. Especially the gold(I) complexes can form colloidal nanoparticles, which makes them attractive for biological applications. The gold(I) complex with 1,5-bis(p-tolyl)-3,7-bis(pyridin-2-yl)-1,5-diaza-3,7-diphosphacyclooctane as ligand ([AuCl)2L]) forms core-shell type nanoparticles with polyethyleneimine (PEI) in aqueous solution which could be employed for cell staining (bioimaging).
Projektbezogene Publikationen (Auswahl)
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Intracyclic iron(II) complexes based on 16-membered P 4 N 2 corands. Phosphorus, Sulfur, and Silicon and the Related Elements 194 (2019) 438-439.
T. I. Wittmann, E. I. Musina, E. Hey-Hawkins & A. Karasik
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Self‐Assembly of Chiral 1,8‐Diaza‐3,6,10,13‐tetraphosphacyclotetradecanes via Dynamic Transformation of 7‐ and 14‐Membered Aminomethylphosphines. European Journal of Inorganic Chemistry, 2019(26), 3053-3060.
Musina, Elvira; Wittmann, Tatiana; Latypov, Shamil; Kondrashova, Svetlana; Lönnecke, Peter; Litvinov, Igor; Hey‐Hawkins, Evamarie & Karasik, Andrey
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Copper(II) Complexes with N,O-Hybrid Ligands based on Pyridyl-Containing Phospholane Oxides. Russian Journal of Coordination Chemistry, 46(9), 600-607.
Trigulova, K. R.; Shamsieva, A. V.; Faizullin, R. R.; Lönnecke, P.; Hey-Hawkins, E.; Voloshina, A. D.; Musina, E. I. & Karasik, A. A.
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Dynamic Covalent Chemistry Approach toward 18-Membered P4N2 Macrocycles and Their Nickel(II) Complexes. The Journal of Organic Chemistry, 85(22), 14610-14618.
Musina, Elvira I.; Wittmann, Tatiana I.; Musin, Lenar I.; Balueva, Anna S.; Shpagina, Alena S.; Litvinov, Igor A.; Lönnecke, Peter; Hey-Hawkins, Evamarie; Karasik, Andrey A. & Sinyashin, Oleg G.
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New Gold(I) Complexes with 1,5-Diaza-3,7-Diphosphacyclooctanes: Synthesis and Structures. Russian Journal of Coordination Chemistry, 46(7), 477-484.
Spiridonova, Yu. S.; Strelnik, I. D.; Musina, E. I.; Hey-Hawkins, E.; Litvinov, I. A. & Karasik, A. A.
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Stereoselective synthesis of the RPSPSPRP isomer of 22-membered P4N2 macrocycles. Mendeleev Communications, 30(6), 697-699.
Musina, Elvira I.; Wittmann, Tatiana I.; Shpagina, Alena S.; Karasik, Andrey A.; Lönnecke, Peter & Hey-Hawkins, Evamarie
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Triple-bridged helical binuclear copper(i) complexes: Head-to-head and head-to-tail isomerism and the solid-state luminescence. Dalton Transactions, 49(34), 11997-12008.
Shamsieva, Aliia V.; Musina, Elvira I.; Gerasimova, Tatiana P.; Strelnik, Igor D.; Strelnik, Anna G.; Kolesnikov, Ilya E.; Kalinichev, Alexey A.; Islamov, Daut R.; Samigullina, Aida I.; Lönnecke, Peter; Katsyuba, Sergey A.; Hey-Hawkins, Evamarie; Karasik, Andrey A. & Sinyashin, Oleg G.
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Assembly of Heterometallic AuICu2I2 Cores on the Scaffold of NPPN-Bridging Cyclic Bisphosphine. Inorganic Chemistry, 60(7), 5402-5411.
Dayanova, Irina R.; Shamsieva, Aliia V.; Strelnik, Igor D.; Gerasimova, Tatiana P.; Kolesnikov, Ilya E.; Fayzullin, Robert R.; Islamov, Daut R.; Saifina, Alina F.; Musina, Elvira I.; Hey-Hawkins, Evamarie & Karasik, Andrey A.
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Deep-Blue Emissive Copper(I) Complexes Based on P-Thiophenylethyl-Substituted Cyclic Bisphosphines Displaying Photoinduced Structural Transformations of the Excited States. Inorganic Chemistry, 61(42), 16596-16606.
Strelnik, Igor D.; Dayanova, Irina; Gerasimova, Tatiana P.; Katsyuba, Sergey A.; Kolesnikov, Ilya E.; Kalinichev, Alexey; Shmelev, Artemiy; Islamov, Daut R.; Lönnecke, Peter; Hey-Hawkins, Evamarie; Musina, Elvira I. & Karasik, Andrey A.
