TY - JOUR A1 - Ast, S. A1 - Fischer, Tobias A1 - Müller, H. A1 - Mickler, W. A1 - Schwichtenberg, M. A1 - Rurack, Knut A1 - Holdt, H.-J. T1 - Integration of the 1,2,3-triazole 'click' motif as a potent signalling element in metal ion responsive fluorescent probes JF - Chemistry - A European journal N2 - In a systematic approach we synthesized a new series of fluorescent probes incorporating donor–acceptor (D-A) substituted 1,2,3-triazoles as conjugative π-linkers between the alkali metal ion receptor N-phenylaza-[18]crown-6 and different fluorophoric groups with different electron-acceptor properties (4-naphthalimide, meso-phenyl-BODIPY and 9-anthracene) and investigated their performance in organic and aqueous environments (physiological conditions). In the charge-transfer (CT) type probes 1, 2 and 7, the fluorescence is almost completely quenched by intramolecular CT (ICT) processes involving charge-separated states. In the presence of Na+ and K+ ICT is interrupted, which resulted in a lighting-up of the fluorescence in acetonitrile. Among the investigated fluoroionophores, compound 7, which contains a 9-anthracenyl moiety as the electron-accepting fluorophore, is the only probe which retains light-up features in water and works as a highly K+/Na+-selective probe under simulated physiological conditions. Virtually decoupled BODIPY-based 6 and photoinduced electron transfer (PET) type probes 3–5, where the 10-substituted anthracen-9-yl fluorophores are connected to the 1,2,3-triazole through a methylene spacer, show strong ion-induced fluorescence enhancement in acetonitrile, but not under physiological conditions. Electrochemical studies and theoretical calculations were used to assess and support the underlying mechanisms for the new ICT and PET 1,2,3-triazole fluoroionophores. KW - Charge transfer KW - Click chemistry KW - Electron transfer KW - Fluorescent probes KW - Metal ions PY - 2013 DO - https://doi.org/10.1002/chem.201201575 SN - 0947-6539 SN - 1521-3765 VL - 19 IS - 9 SP - 2990 EP - 3005 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-27742 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Debatin, F. A1 - Behrens, K. A1 - Weber, J. A1 - Baburin, I. A. A1 - Thomas, A. A1 - Schmidt, J. A1 - Senkovska, I. A1 - Kaskel, S. A1 - Kelling, A. A1 - Hedin, N. A1 - Bacsik, Z. A1 - Leoni, S. A1 - Seifert, G. A1 - Jäger, Christian A1 - Günter, C. A1 - Schilde, U. A1 - Friedrich, A. A1 - Holdt, H.-J. T1 - An isoreticular family of microporous metal-organic frameworks based on zinc and 2-substituted imidazolate-4-amide-5-imidate: syntheses, structures and properties JF - Chemistry - A European journal N2 - We report on a new series of isoreticular frameworks based on zinc and 2-substituted imidazolate-4-amide-5-imidate (IFP-1–4, IFP=imidazolate framework Potsdam) that form one-dimensional, microporous hexagonal channels. Varying R in the 2-substitued linker (R=Me (IFP-1), Cl (IFP-2), Br (IFP-3), Et (IFP-4)) allowed the channel diameter (4.0–1.7 Å), the polarisability and functionality of the channel walls to be tuned. Frameworks IFP-2, IFP-3 and IFP-4 are isostructural to previously reported IFP-1. The structures of IFP-2 and IFP-3 were solved by X-ray crystallographic analyses. The structure of IFP-4 was determined by a combination of PXRD and structure modelling and was confirmed by IR spectroscopy and 1H MAS and 13C CP-MAS NMR spectroscopy. All IFPs showed high thermal stability (345–400°C); IFP-1 and IFP-4 were stable in boiling water for 7 d. A detailed porosity analysis was performed on the basis of adsorption measurements by using various gases. The potential of the materials to undergo specific interactions with CO2 was investigated by measuring the isosteric heats of adsorption. The capacity to adsorb CH4 (at 298 K), CO2 (at 298 K) and H2 (at 77 K) at high pressure were also investigated. In situ IR spectroscopy showed that CO2 is physisorbed on IFP-1–4 under dry conditions and that both CO2 and H2O are physisorbed on IFP-1 under moist conditions. KW - Adsorption KW - Metal-organic frameworks KW - Microporous materials KW - N,O ligands KW - Zinc PY - 2012 DO - https://doi.org/10.1002/chem.201200889 SN - 0947-6539 SN - 1521-3765 VL - 18 IS - 37 SP - 11630 EP - 11640 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-27725 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Debatin, F. A1 - Thomas, A. A1 - Kelling, A. A1 - Hedin, N. A1 - Bacsik, Z. A1 - Senkovska, I. A1 - Kaskel, S. A1 - Junginger, M. A1 - Müller, H. A1 - Schilde, U. A1 - Jäger, Christian A1 - Friedrich, A. A1 - Holdt, H.-J. T1 - In situ synthesis of an imidazolate-4-amide-5-imidate ligand and formation of a microporous zinc-organic framework with H2-and CO2-storage ability JF - Angewandte Chemie / International Edition KW - Metal-organic framework KW - Synthesis KW - XRD KW - FTIR KW - NMR KW - Gas sorption KW - Microporous materials KW - N,O ligands KW - Solvothermal synthesis PY - 2010 DO - https://doi.org/10.1002/anie.200906188 SN - 1433-7851 SN - 1521-3773 SN - 0570-0833 VL - 49 IS - 7 SP - 1258 EP - 1262 PB - Wiley-VCH CY - Weinheim AN - OPUS4-21132 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kammer, S. A1 - Kelling, A. A1 - Baier, H. A1 - Mickler, W. A1 - Dosche, C. A1 - Rurack, Knut A1 - Kapp, A. A1 - Lisdat, F. A1 - Holdt, H.-J. T1 - 2,11-dialkylated 1,12-diazaperylene copper(I) complexes: First supramolecular column assemblies by Pi-Pi stacking between homoleptic tetrahedral metal complexes, exhibiting low-energy MLCT transitions JF - European journal of inorganic chemistry KW - Copper KW - N ligands KW - Pi interactions KW - Self-assembly KW - Immobilization PY - 2009 DO - https://doi.org/10.1002/ejic.200900695 SN - 1434-1948 SN - 1099-0682 VL - 2009 IS - 31 SP - 4648 EP - 4659 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-20286 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -