TY - JOUR A1 - García-Acosta, B. A1 - Comes, M. A1 - Bricks, J.L. A1 - Kudinova, M.A. A1 - Kurdyukov, V.V. A1 - Tolmachev, A.I. A1 - Descalzo López, Ana Belén A1 - Marcos, M. Dolores A1 - Martínez-Mánez, Ramon A1 - Moreno, A. A1 - Sancenón, F. A1 - Soto, J. A1 - Villaescusa, L.A. A1 - Rurack, Knut A1 - Barat, J. M. A1 - Escriche, I. A1 - Amorós, P. T1 - Sensory hybrid host materials for the selective chromo-fluorogenic detection of biogenic amines KW - Biogene Amine KW - Histamin KW - Farbreaktion KW - Pyralium-Farbstoffe KW - Fluoreszenz KW - Hybrid-Materialien PY - 2006 SN - 0022-4936 SN - 0009-241x SN - 1359-7345 SN - 1364-548x IS - 21 SP - 2239 EP - 2241 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-12563 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Descalzo López, Ana Belén A1 - Martínez-Mánez, Ramon A1 - Sancenón, F. A1 - Hoffmann, Katrin A1 - Rurack, Knut T1 - The Supramolecular Chemistry of Organic-Inorganic Hybrid Materials N2 - The combination of nanomaterials as solid supports and supramolecular concepts has led to the development of hybrid materials with improved functionalities. These hetero-supramolecular ideas provide a means of bridging the gap between molecular chemistry, materials sciences, and nanotechnology. In recent years, relevant examples have been reported on functional aspects, such as enhanced recognition and sensing by using molecules on preorganized surfaces, the reversible building of nanometer-sized networks and 3D architectures, as well as biomimetic and gated chemistry in hybrid nanomaterials for the development of advanced functional protocols in three-dimensional frameworks. This approach allows the fine-tuning of the properties of nanomaterials and offers new perspectives for the application of supramolecular concepts. KW - Aggregation KW - Mesoporous materials KW - Molecular recognition KW - Nanoparticles KW - Sensors PY - 2006 DO - https://doi.org/10.1002/anie.200600734 SN - 1433-7851 SN - 1521-3773 SN - 0570-0833 VL - 45 IS - 36 SP - 5924 EP - 5948 PB - Wiley-VCH CY - Weinheim AN - OPUS4-12824 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Martínez-Mánez, Ramon A1 - Sancenón, F. A1 - Descalzo López, Ana Belén A1 - Rurack, Knut ED - Abd-El Aziz, Alaa S. ED - Carraher, Charles E. ED - Pittman, Charles U. ED - Zeldin, Martel T1 - Supramolecular hybrid materials - integrating functionality with sensing KW - Biochemie KW - Biomakromoleküle KW - DNA KW - Gold KW - Hybridmaterialien KW - Nanopartikel KW - Quantenpunkte KW - Selbstorganisation KW - Sensorik KW - Silica KW - Supramolekulare Chemie PY - 2009 SN - 978-0-470-25144-7 SN - 1545-438X VL - 9 SP - 369 EP - 405 PB - John Wiley & Sons CY - Hoboken, New Jersey, USA AN - OPUS4-20318 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - García-Acosta, B. A1 - Martínez-Mánez, Ramon A1 - Sancenón, F. A1 - Soto, J. A1 - Rurack, Knut A1 - Spieles, Monika A1 - García-Breijo, E. A1 - Gil, L. T1 - Ditopic N-Crowned 4-(p-Aminophenyl)-2,6-diphenylpyridines: Implications of Macrocycle Topology on the Spectroscopic Properties, Cation Complexation, and Differential Anion Responses N2 - A family of N-crowned 4-p-(aminophenyl)-2,6-diphenylpyridines DA (1-6) has been synthezised, characterized, and studied as potential hosts for the signaling of cationic and anionic guests. The ditopic probes contain two coordination sites, a monodentate 2,6-diphenylpyridine and an anilino group with macrocycles of different ring size, denticity, and type of secondary heteroatom (O and/or S). X-ray structure analysis of aza-oxa-thia-crowned 5 indicated a largely planar chromophore. Optical spectroscopic and electrochemical studies revealed that the anilino-type donor (D) and the 2,6-diphenylpyridine acceptor (A) are strongly -conjugated, entailing intense intramolecular charge-transfer absorption bands at 340 nm. Binding studies with protons and metal ions (M = Cu2+, Zn2+, Hg2+, Fe3+, Pb2+, Ni2+, Cd2+) showed shifts of the band to the visible (440 nm) when coordination at the pyridine group occurs, strengthening its acceptor character. In contrast, no band in the visible is formed if binding takes place at the anilino group. Three different responses were found for various pairs of DA and M: selective metal coordination to D or A as well as coordination at both sites. A selective response was found for 5 and Hg2+. Because of the multitude of coordination-induced effects, the DA-M ensembles were further employed for differential anion sensing. In this protocol, the addition of an anion X to a certain, weakly coordinated DA-M can (i) lead to the formation of a ternary ion pair complex (DA-M-X), (ii) change the preference for A or D coordination, (iii) induce dissociation of the complex, or (iv) can have no effect. Various patterns of absorption changes were obtained as a result of different responses (i)-(iv) of the DA-M's in the presence of various X's. Data analysis yielded recognition patterns for acetate, F- and CN-, demonstrating the potential of simple chromogenic host-guest pairs for differential anion signaling. KW - Fluoreszenz KW - Absorption KW - Molekular Logik KW - Farbstoffe PY - 2007 DO - https://doi.org/10.1021/ic062069z SN - 0020-1669 SN - 1520-510X VL - 46 IS - 8 SP - 3123 EP - 3135 PB - American Chemical Society CY - Washington, DC AN - OPUS4-16084 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lozano-Torres, B. A1 - Marcos, M. Dolores A1 - Pardo, T. A1 - Sancenón, F. A1 - Martínez-Mánez, Ramon A1 - Rurack, Knut T1 - Anilinopyridine–metal complexes for the selective chromogenic sensing of cyanide anion N2 - Probe 1, which contains an anilinopyridine chromophore and an azaoxa macrocyclic subunit, presented an absorption band centered at 340 nm in acetonitrile. Addition of Fe(III), Cr(III) and Hg(II) induced the growth of a new absorption band at 430 nm (with color change from colorless to yellow), whereas in the presence of Cu(II), Zn(II) and Pb(II), less marked changes were observed. The color changes observed upon addition of Fe(III), Cr(III) and Hg(II) were ascribed to the formation of 1:1 stoichiometry complexes with probe 1. Coordination of Fe(III), Cr(III) and Hg(II) with the pyridine fragment of 1 induced an enhancement of the charge transfer character accompanied with a marked bathochromic shift that was reflected in a color change from colorless to yellow. The strength of the interaction between probe 1 and Fe(III) cation was modulated upon interaction with anions. Of all the anions tested, only cyanide was able to induce the bleaching of the yellow 1·Fe(III) complex solution. This bleaching was ascribed to the formation of 1·Fe(III)-CN complex that restored, to some extent, the optical features of the free probe allowing the chromogenic sensing of cyanide. Besides, 1·Fe(III) complex was used to detect cyanide in acetonitrile-water 90:10 v/v mixtures with good recoveries. KW - Anilinopyridine KW - Charge Transfer KW - Iron Complex KW - Colorimetric Test KW - Cyanide PY - 2018 DO - https://doi.org/10.1080/00958972.2018.1434719 SN - 0095-8972 VL - 71 IS - 6 SP - 786 EP - 796 PB - Taylor & Francis Group CY - London AN - OPUS4-45398 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ros-Lis, J.V. A1 - Martínez-Mánez, Ramon A1 - Rurack, Knut A1 - Sancenón, F. A1 - Soto, J. A1 - Spieles, Monika T1 - Highly Selective Chromogenic Signaling of Hg2+ in Aqueous Media at Nanomolar Levels Employing a Squaraine-Based Reporter N2 - A chromogenic chemosensor for Hg2+ detection in aqueous media at the nanomolar level has been developed from squaraine scaffoldings. KW - Quecksilber KW - Absorption KW - Fluoreszenz KW - Squarain-Farbstoffe KW - Aggregate KW - Chromoionophor PY - 2004 DO - https://doi.org/10.1021/ic049422q SN - 0020-1669 SN - 1520-510X VL - 43 IS - 17 SP - 5183 EP - 5185 PB - American Chemical Society CY - Washington, DC AN - OPUS4-4124 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ros-Lis, J.V. A1 - Marcos, M. Dolores A1 - Martínez-Mánez, Ramon A1 - Rurack, Knut A1 - Soto, J. T1 - Ein regeneratives Chemodosimeter für die hoch selektive und empfindliche optische Bestimmung von Hg2+, basierend auf der metallinduzierten Bildung eines Farbstoffes KW - Fluorometrischer Nachweis KW - Chromogener Nachweis KW - Quecksilber KW - Chemodosimeter PY - 2005 SN - 0044-8249 SN - 0932-2140 SN - 1521-3757 VL - 117 IS - 28 SP - 4479 EP - 4482 PB - Wiley-VCH CY - Weinheim AN - OPUS4-10379 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ros Lis, J.V. A1 - Martínez-Mánez, Ramon A1 - Rurack, Knut A1 - Soto, J. T1 - A regenerative chemodosimeter based on metal-induced dye formation for the highly selective and sensitive optical detection of Hg2+ KW - Chemodosimeter KW - Chromogener Nachweis KW - Fluormetrischer Nachweis KW - Quecksilber PY - 2005 DO - https://doi.org/10.1002/anie.200500583 SN - 1433-7851 SN - 1521-3773 SN - 0570-0833 N1 - Sprachen: Deutsch/Englisch - Languages: German/English VL - 44 SP - 4405 EP - 4407 PB - Wiley-VCH CY - Weinheim AN - OPUS4-11006 LA - mul AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ros-Lis, J.V. A1 - Martínez-Mánez, Ramon A1 - Sancenón, F. A1 - Soto, J. A1 - Spieles, Monika A1 - Rurack, Knut T1 - Aquaraines as reporter units: insights into their photophysics, protonation, and metal-ion coordination behaviour KW - Dyes/pigments KW - Fluorescence KW - Metal ions KW - Protonation KW - Squaraines KW - Farbstoffe KW - Fluoreszenz KW - Metallionen KW - Protonierung PY - 2008 DO - https://doi.org/10.1002/chem.200800300 SN - 0947-6539 SN - 1521-3765 VL - 14 SP - 10101 EP - 10114 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-18444 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Calero, P. A1 - Hecht, Mandy A1 - Martínez-Mánez, Ramon A1 - Sancenón, F. A1 - Soto, J. A1 - Vivancos, J.L. A1 - Rurack, Knut T1 - Silica nanoparticles functionalised with cation coordination sites and fluorophores for the differential sensing of anions in a quencher displacement assay (QDA) N2 - In conjunction with quenching metal ions, silica nanoparticles carrying terpyridine coordination sites and sulforhodamine B signalling units were employed for the differential fluorometric recognition of anions. KW - Hybridmaterial KW - Silica-Nanopartikel KW - Fluoreszenz KW - Anionen KW - Verdrängungsassay PY - 2011 DO - https://doi.org/10.1039/c1cc13039k SN - 0022-4936 SN - 0009-241x SN - 1359-7345 SN - 1364-548x VL - 47 IS - 38 SP - 10599 EP - 10601 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-24489 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ros Lis, J.V. A1 - Martínez-Mánez, Ramon A1 - Rurack, Knut A1 - Soto, J. T1 - A regenerative chemodosimeter based on metal-induced dye formation for the highly selective and sensitive optical detection of Hg2+ KW - Fluormetrischer Nachweis KW - Chromogener Nachweis KW - Quecksilber KW - Chemodosimeter PY - 2005 DO - https://doi.org/10.1002/ange.200500583 SN - 0044-8249 SN - 0932-2140 SN - 1521-3757 VL - 117 SP - 4479 EP - 4482 PB - Wiley-VCH CY - Weinheim AN - OPUS4-7282 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Climent Terol, Estela A1 - Marcos, D. A1 - Martínez-Mánez, Ramon A1 - Sancenón, F. A1 - Soto, J. A1 - Rurack, Knut A1 - Amorós, P. T1 - The determination of methylmercury in real samples using organically capped mesoporous inorganic materials capable of signal amplification KW - Chemosensors KW - Fluorescence KW - Mesoporous materials KW - Methylmercury KW - Methylquecksilber KW - Sensoren KW - Mesoporöse Materialien KW - Fluoreszenz KW - Hybridmaterialien PY - 2009 DO - https://doi.org/10.1002/anie.200904243 SN - 1433-7851 SN - 1521-3773 SN - 0570-0833 VL - 48 IS - 45 SP - 8519 EP - 8522 PB - Wiley-VCH CY - Weinheim AN - OPUS4-20308 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Martínez-Mánez, Ramon A1 - Sancenón, F. A1 - Hecht, Mandy A1 - Biyikal, Mustafa A1 - Rurack, Knut T1 - Nanoscopic optical sensors based on functional supramolecular hybrid materials N2 - This review highlights how the combination of supramolecular principles and nanoscopic solid structures enables the design of new hybrid sensing ensembles with improved sensitivity and/or selectivity and for the targeting of analytes for which selectivity is hard to achieve by conventional methods. Such ideas are bridging the gap between molecules, materials sciences and nanotechnology. Relevant examples will be detailed, taking into account functional aspects such as (1) enhanced coordination of functionalized solids, (2) enhanced signalling through preorganization, (3) signalling by assembly–disassembly of nanoscopic objects, (4) biomimetic probes utilizing discrimination by polarity and size and (5) distinct switching and gating protocols. These strategies are opening new prospects for sensor research and signalling paradigms at the frontier between nanotechnology, smart materials and supramolecular chemistry. KW - Supramolecular chemistry KW - Optical probes KW - Nanotechnology KW - Hybrid organic-inorganic materials PY - 2011 DO - https://doi.org/10.1007/s00216-010-4198-2 SN - 1618-2642 SN - 1618-2650 VL - 399 IS - 1 SP - 55 EP - 74 PB - Springer CY - Berlin AN - OPUS4-22908 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Descalzo, Ana B. A1 - Martínez-Mánez, Ramon A1 - Radeglia, Reiner A1 - Rurack, Knut A1 - Soto, J. T1 - Coupling Selectivity with Sensitivity in an Integrated Chemosensor Framework: Design of a Hg2+-Responsive Probe, Operating above 500 nm N2 - For the highly selective and sensitive sensing of Hg2+ in water, a new design concept was realized where the selectivity of the probe's binding site is amplified by electronic properties of the chromophore. The molecular architecture of this phenoxazinone-type sensor molecule combines two potential coordination sites via an amino-keto conjugative backbone. These structural prerequisites allow only the most preferred mercuric ion to bind to the dithia dioxa monoaza crown unit, while other heavy, transition, and main group metal ions as well as protons are trapped at the keto group, inducing opposite spectral effects due to interaction with either the donor (Hg2+) or the acceptor group (other cations) of the probe. Besides these advantageous features, the probe operates well within the visible range of the spectrum and displays rather intense molar absorptivities as well as fluorescence quantum yields. PY - 2003 DO - https://doi.org/10.1021/ja0290779 SN - 0002-7863 SN - 1520-5126 VL - 125 IS - 12 SP - 3418 EP - 3419 PB - American Chemical Society CY - Washington, DC AN - OPUS4-2377 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - García-Acosta, B. A1 - Albiach-Martí, X. A1 - García, E. A1 - Gil, R. A1 - Martínez-Mánez, Ramon A1 - Rurack, Knut A1 - Sancenón, F. A1 - Soto, J. T1 - Coordinative and electrostatic forces in action: from the design of differential chromogenic anion sensors to selective carboxylate recognition N2 - A new family of differential chromogenic anion chemosensors is described based on anilinopyridine–metal cation coordinative signalling ensembles KW - Differentielle Sensoren KW - Anionen KW - Carboxylat KW - Chromogene Sensoren KW - Koordinative Bindungen KW - Elektrostatische Wechselwirkungen PY - 2004 DO - https://doi.org/10.1039/b314997h SN - 0022-4936 SN - 0009-241x SN - 1359-7345 SN - 1364-548x IS - 7 SP - 774 EP - 775 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-3438 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Descalzo López, Ana Belén A1 - Marcos, M. Dolores A1 - Monte, Christian A1 - Martínez-Mánez, Ramon A1 - Rurack, Knut T1 - Mesoporous silica materials with covalently anchored phenoxazinone dyes as fluorescent hybrid materials for vapour sensing KW - Anorganisch-organische Hybridmaterialien KW - Sensorik KW - Fluoreszenz KW - Flüchtige organische Verbindungen PY - 2007 DO - https://doi.org/10.1039/b707473e SN - 0959-9428 SN - 1364-5501 VL - 17 SP - 4716 EP - 4723 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-16139 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Rurack, Knut A1 - Martínez-Mánez, Ramon ED - Charles M. Lukehart, ED - Robert A. Scott, T1 - Biomimetic chemistry of hybrid materials N2 - The article discusses representative examples published in the field of functional biomimetic chemistry of hybrid materials between 2004 and mid-2007. First, we focus on the modification of morphological aspects of (bio)organic–inorganic hybrid materials to create sophisticated gating and switching mechanisms. The architecture of the systems is presented and the elements of control by external stimuli that have been established in recent years, such as optical, electrochemical, chemical, thermal, or magnetic means, are described. Various functions ranging from (site-specific) delivery to indication at the nanometric level are reported. Next we develop the idea of utilizing hybrid frameworks for biomimetic signaling inspired by the way nature has created binding pockets and the concept of induced-fit. Such a merging of inorganic scaffolds with supramolecular concepts results in enhanced molecular recognition and signaling. Finally selected recent advances in the field of hybrid biomimetic motors both of linear and rotary types are presented. The contribution shows how novel biomimetic functions can arise from synergisms between specifically designed hybrid materials and the implementation of supramolecular and/or bioorganic concepts. KW - Biochemie KW - Biomimetika KW - DNA KW - Gold KW - Hybridmaterialien KW - Molekulare Schalter KW - Molekulare Motoren KW - Nanopartikel KW - Quantenpunkte KW - Schalter KW - Sensorik KW - Silica KW - Supramolekulare Chemie PY - 2008 SN - 978-0470-51644-7 SP - 31 EP - 50 PB - Wiley CY - Chichester AN - OPUS4-19213 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Rurack, Knut A1 - Martínez-Mánez, Ramon ED - Robert H. Crabtree, T1 - Functional supramolecular hybrid materials N2 - The combination of suitable nanoscopic inorganic supports with supramolecular concepts and bioconjugation strategies opens up exciting perspectives for the development of bioinorganic and organic–inorganic hybrid materials with improved functionalities. Many of the examples from the period 2004 to mid-2007 reviewed here bridge the gap between molecules, materials sciences, biochemistry, and nanotechnology. The synergistic use of these approaches has led to the advancement of various functions such as enhanced recognition, amplified signaling, the controlled assembly and disassembly of aggregates and 3-D architectures. Many of the implemented active functions can be carried out in a reversible and directed fashion on purpose by triggering with an external stimulus. These ideas bring tunability to properties of inorganic solids and new perspectives of application to biochemical and supramolecular concepts. Classic inorganic chemistries such as metal or semiconductor nanoparticles, silica or carbon materials, and coordination chemistry are thus elevated to another level of sophistication and contribute significantly to frontier research areas in directed transport and delivery, nanoelectronics and mechanics, chip technology, smart materials, memory devices, and bioanalytics. KW - Biochemie KW - Biomakromoleküle KW - DNA KW - Gold KW - Hybridmaterialien KW - Nanopartikel KW - Quantenpunkte KW - Selbstorganisation KW - Sensorik KW - Silica KW - Supramolekulare Chemie PY - 2009 DO - https://doi.org/10.1002/0470862106.ia400 SP - 1 EP - 23 PB - Wiley CY - Chichester AN - OPUS4-19847 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - BOOK A1 - Rurack, Knut A1 - Martínez-Mánez, Ramon T1 - Biomimetic chemistry of hybrid materials N2 - The article discusses representative examples published in the field of functional biomimetic chemistry of hybrid materials between 2004 and mid-2007. First, we focus on the modification of morphological aspects of (bio)organic–inorganic hybrid materials to create sophisticated gating and switching mechanisms. The architecture of the systems is presented and the elements of control by external stimuli that have been established in recent years, such as optical, electrochemical, chemical, thermal, or magnetic means, are described. Various functions ranging from (site-specific) delivery to indication at the nanometric level are reported. Next we develop the idea of utilizing hybrid frameworks for biomimetic signaling inspired by the way nature has created binding pockets and the concept of induced-fit. Such a merging of inorganic scaffolds with supramolecular concepts results in enhanced molecular recognition and signaling. Finally selected recent advances in the field of hybrid biomimetic motors both of linear and rotary types are presented. The contribution shows how novel biomimetic functions can arise from synergisms between specifically designed hybrid materials and the implementation of supramolecular and/or bioorganic concepts. KW - Biochemie KW - Biomimetika KW - DNA KW - Gold KW - Hybridmaterialien KW - Molekulare Schalter KW - Molekulare Motoren KW - Nanopartikel KW - Quantenpunkte KW - Schalter KW - Sensorik KW - Silica KW - Supramolekulare Chemie PY - 2009 DO - https://doi.org/10.1002/0470862106.ia420 SP - 1 EP - 20 PB - Wiley CY - Chichester AN - OPUS4-19846 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ros-Lis, J.V. A1 - Martínez-Mánez, Ramon A1 - Sancenón, F. A1 - Soto, J. A1 - Rurack, Knut A1 - Weißhoff, Hardy T1 - Signalling Mechanisms in Anion-Responsive Push-Pull Chromophores: The Hydrogen-Bonding, Deprotonation and Anion-Exchange Chemistry of Functionalized Azo Dyes N2 - A family of azo dyes containing amide (1), urea (2), thiourea (3), carbamate (4) or amino (5) hydrogen-bond donating groups were synthesized and their response toward anions was studied. Acetonitrile solutions of 1-5 show bright yellow colours, due to charge-transfer bands in the 375-400 nm region, slightly modulated by the electron donor strength of the group attached to the 4 end of the 4-nitroazobenzene scaffold. Anions of different shape and size (i.e., spherical F-,Cl-, Br- and I-, planar and tetrahedral oxoanions such as NO3-, H2PO4- and HSO4-, carboxylates such as acetate and benzoate and the linear anions cyanide and thiocyanate) were employed in the recognition studies. Two different effects were distinguished: (i) bathochromic shifts of <40 nm to pale orange, due to anion coordination, and (ii) strong red shifts of ca. 200 nm with a concomitant colour change to blue, due to deprotonation. This behaviour was explained as a balance between the deprotonation tendency of the binding sites in the different receptors and the proton affinities of the anions. Semiempirical calculations were carried out to evaluate the hydrogen bond-donating abilities of the anions and the dyes and a good correlation with the experimentally found values was observed. Stability constants for the receptor-anion complexes were determined spectrophotometrically and the different responses toward fluoride and acetate were assessed by NMR titration experiments. Finally, as a special case, we also report the use of this family of compounds as colorimetric carbon dioxide sensors through reaction with the unprotonated forms of the azo dyes. KW - Chromophores KW - Dyes/Pigments KW - Chemosensors KW - Gas sensors KW - Carbon dioxide PY - 2007 DO - https://doi.org/10.1002/ejoc.200601111 SN - 1434-193X SN - 1099-0690 VL - 2007 IS - 15 SP - 2449 EP - 2458 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-16081 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ros-Lis, J.V. A1 - Martínez-Mánez, Ramon A1 - Soto, J. A1 - Villaescusa, L.A. A1 - Rurack, Knut T1 - Squaraine 'ships' in the Y zeolite 'bottle': a chromogenic sensing material for the detection of volatile amines and thiols N2 - The inclusion of squaraine (SQ) dye I into the supercages of zeolite Y (structure code FAU) with a SiO2/Al2O3 ratio of 30 (Z30) through a two-step ship-in-the-bottle approach is reported, resulting in the squaraine-containing hybrid material Z30-SQ. Attempts to use the same synthetic procedure on sodium and ammonium Y zeolites were unsuccessful, stressing the importance of the presence of Brønsted acid centres in the Z30 zeolite. The reflectance spectra of Z30-SQ show a maximum in the typical squaraine monomer region at 618 nm and a shoulder at 570 nm. Spectral analyses revealed that the major species are SQ dimers and (tightly adsorbed) SQ monomers and SQ aggregates are only formed to a minor degree. The emission spectrum of Z30-SQ shows a single band at 669 nm. The sensory performance of this material was tested in the presence of volatile propylamine and propylthiol and other volatile organic compounds (acetone, ethanol, dichloromethane, hexane, acetonitrile, ethyl acetate, ethyl ether and acetic acid). The blue Z30-SQ material reacts with the thiol and amine derivatives, resulting in the bleaching of the solid and disappearance of the absorption band in the visible region, but does not undergo spectroscopic changes in the presence of other volatile organic compounds (VOCs). Whereas the reaction with propylamine is irreversible, a partial reversibility was found in the presence of the thiol. Theoretical investigations of the reactivity of I with several VOC molecules at the semi-empirical level reproduced well the experimentally observed reactivity. KW - Fluoreszenz KW - Gassensorik KW - Squarain-Farbstoffe KW - Zeolite PY - 2011 DO - https://doi.org/10.1039/c0jm03780j SN - 0959-9428 SN - 1364-5501 VL - 21 IS - 13 SP - 5004 EP - 5010 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-23480 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -