TY - JOUR A1 - Röhr, Holger A1 - Trieflinger, C. A1 - Rurack, Knut A1 - Daub, J. T1 - Proton- and Redox-Controlled Switching of Photo- and Electrochemiluminescence in Thiophenyl-Substituted Boron-Dipyrromethene Dyes N2 - A luminescent molecular switch in which the active thiol/disulfide switching element is attached to a meso-phenyl-substituted boron-dipyrromethene (BDP) chromophore as the signalling unit is presented. The combination of these two functional units offers great versatility for multimodal switching of luminescence: 1) deprotonation/protonation of the thiol/thiolate moiety allows the highly fluorescent meso-p-thiophenol-BDP and its nonfluorescent thiolate analogue to be chemically and reversibly interconverted, 2) electrochemical oxidation of the monomeric dyes yields the fluorescent disulfide-bridged bichromophoric dimer, also in a fully reversible process, and 3) besides conventional photoexcitation, the well separated redox potentials of the BDP also allow the excited BDP state to be generated electrochemically (i.e., processes 1) and 2) can be employed to control both photo- and electrochemiluminescence (ECL) of the BDP). The paper introduces and characterizes the various states of the switch and discusses the underlying mechanisms. Investigation of the ortho analogue of the dimer provided insight into potential chromophore-chromophore interactions in such bichromophoric architectures in both the ground and the excited state. Comparison of the optical and redox properties of the two disulfide dimers further revealed structural requirements both for redox switches and for ECL-active molecular ensembles. By employing thiol/disulfide switching chemistry and BDP luminescence features, it was possible to create a prototype molecular ensemble that shows both fully reversible proton- and redox-gated electrochemiluminescence. KW - Boron-dipyrromethene KW - Electrochemiluminescence KW - Fluorescence KW - Molecular switches KW - Redox chemistry KW - Thiol/disulfide chemistry KW - Fluoreszenz KW - Elektrochemilumineszenz KW - Redox-Kontrolle KW - Molekulare Sensoren PY - 2006 DO - https://doi.org/10.1002/chem.200500729 SN - 0947-6539 SN - 1521-3765 VL - 12 IS - 3 SP - 689 EP - 700 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-12175 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Trieflinger, C. A1 - Rurack, Knut A1 - Daub, J. T1 - "Turn ON/OFF your LOV light": Bordipyrromethen-Flavin-Dyaden als biomimetische, von der LOV-Domäne abgeleitete Schalter KW - Boron-dipyrromethene KW - Flavin KW - Thiol/disulfide KW - Fluorescence KW - Molecular switching KW - Photoreceptor mimicks PY - 2005 SN - 0044-8249 SN - 0932-2140 SN - 1521-3757 VL - 117 IS - 15 SP - 2328 EP - 2331 PB - Wiley-VCH CY - Weinheim AN - OPUS4-7305 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rurack, Knut A1 - Trieflinger, C. A1 - Kovalchuck, Anton V. A1 - Daub, J. T1 - An ionically driven molecular IMPLICATION gate operating in fluorescence Mode N2 - An asymmetrically core-extended boron-dipyrromethene (BDP) dye was equipped with two electron-donating macrocyclic binding units with different metal ion preferences to operate as an ionically driven molecular IMPLICATION gate. A Na+-responsive tetraoxa-aza crown ether (R2) was integrated into the extended π system of the BDP chromophore to trigger strong intramolecular charge transfer (ICT2) fluorescence and guarantee cation-induced spectral shifts in absorption. A dithia-oxa-aza crown (R1) that responds to Ag+ was attached to the meso position of BDP in an electronically decoupled fashion to independently control a second ICT1 process of a quenching nature. The bifunctional molecule is designed in such a way that in the absence of both inputs, ICT1 does not compete with ICT2 and a high fluorescence output is obtained (InA=InB=0→Out=1). Accordingly, binding of only Ag+ at R1 (InA=1, InB=0) as well as complexation of both receptors (InA=InB=1) also yields Out=1. Only for the case in which Na+ is bound at R2 and R1 is in its free state does quenching occur, which is the distinguishing characteristic for the InA=0 and InB=1→Out=0 state that is required for a logic IMPLICATION gate and Boolean operations such as IF-THEN or NOT. KW - Charge transfer KW - Dyes/pigments KW - Fluorescence KW - Logic gates KW - Molecular devices PY - 2007 DO - https://doi.org/10.1002/chem.200700858 SN - 0947-6539 SN - 1521-3765 VL - 13 IS - 32 SP - 8998 EP - 9003 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-16085 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -