Novel molecular building blocks based on bodipy chromophore: applications in metallosupramolecular polymers and ion sensing

Download
2008
Büyükçakır, Onur
We have designed and synthesized boradiazaindacene (BODIPY) derivatives, appropriately functionalized for metal ion mediated supramolecular polymerization. Thus, ligands for 2- and 2,6-terpyridyl and bipyridyl functionalized BODIPY dyes were synthesized through Sonogashira couplings. These new fluorescent building blocks are responsive to metal ions in a stoichiometry dependent manner. Octahedral coordinating metal ions such as Zn(II), result in polymerization at a stoichiometry which corresponds to two terpyridyl ligands to one Zn(II) ion. However, at increased metal ion concentrations, the dynamic equilibria are re-established in such a way that, monomeric metal complex dominates. The position of equilibria can easily be monitored by 1H NMR and fluorescence spectroscopy. As expected, open shell Fe(II) ions while forming similar complex structures, quench the fluorescence emission of all four functionalized BODIPY ligands.

Suggestions

Novel Molecular Building Blocks Based on the Boradiazaindacene Chromophore: Applications in Fluorescent Metallosupramolecular Coordination Polymers
Bozdemir, Oe. Altan; Buyukcakir, Onur; AKKAYA, Engin Umut (Wiley, 2009-01-01)
We designed and synthesized novel boradiazaindacene (Bodipy) derivatives that are appropriately functionalized for metal-ion-mediated supramolecular polymerization. Thus, ligands for 2-terpyridyl-, 2,6-terpyridyl-. and bipyridyl-functionalized Bodipy dyes were synthesized through Sonogashira couplings. These fluorescent building blocks are responsive to metal ions in a stoichiometry-dependent manner. Octahedral coordinating metal ions such as Zn-II result in polymerization at a stoichiometry corresponding t...
Extraordinary Modes of Bonding Enabled by the Triquinane Framework
Günbaş, Emrullah Görkem (American Chemical Society (ACS), 2013-10-04)
Incorporation of triquinane ring systems into a macrobicyclic framework enables the stabilization of unusual bonding arrangements, including 3-center-2-electron cation, 3-center-3-electron radical, and 3-center-4-electron anion systems, linear divalent fluorine, triplet carbenes, record short C-C bonds, a powerful proton sponge effect, and oxadionium (R4O2+) ions. The means to stabilize and conceivably isolate such species derives from the rigid, convex nature of the triquinane ring system, as well as the s...
Chemoenzymatic synthesis of chiral hydroxymethyl cycloalkenols
Şenocak, Deniz; Demir, Ayhan Sıtkı; Department of Chemistry (2004)
Chiral cyclic alkenols with hydroxymethyl functionality are important structural units in many biologically active natural compouds such as prostaglandins, sesquiterpene antiviral agents, pentenomycins, xanthocidin, sarkomycin, etc. 1,3-cycloalkanediones are converted into bicyclic polyoxo derivatives with formaldehyde and trioxane in the presence of Lewis acid. Selective oxidation of the bicyclic compounds by using manganese(III)acetate followed by enzyme-catalyzed kinetic resolution afforded chiral bicycl...
A new and efficient chemoenzymatic route to both enantiomers of alpha '-acetoxy and alpha '-hydroxy-alpha-methoxy cyclic enones
Demir, Ayhan Sıtkı; Caliskan, Z; Aydin, AE; Bicer, I (Elsevier BV, 2006-03-06)
A chemoenzymatic synthesis of both enantiomers of the pharmacologically interesting alpha'-acetoxy and alpha'-hydroxy-alpha-methoxy cyclic enones starting from alpha-hydroxy cyclic enones is described. Protection of 1,2-diketones, manganese(III) acetate-mediated acetoxylation followed by enzyme-mediated hydrolysis of alpha'-acetoxy enones gives acetoxy enones 3a-d and hydroxy enones 4a-d with high enantiomeric excesses (up to 99%) and good yields. The transesterification of rac-4b in the presence of DMAP af...
Synthesis of heterocyclic amine substituted novel 1,4-Aminoalcohols and applications in various asymmetric transformations
Keskin, Eda; Tanyeli, Cihangir; Department of Chemistry (2007)
Aminoalcohols are very important compounds used in various asymmetric transformations as chiral ligands or chiral auxiliaries. In this thesis, four novel heterocyclic amine substituted chiral 1,4-aminoalcohols were synthesized. In the synthetic strategy, amide esters were synthesized from (2S, 3R)-3-methoxycarbonylbicyclo[2.2.1]hept-5-ene-2-carboxylic acid by DCC coupling method. Subsequent reduction of these amide esters lead to target 1,4-aminoalcohols. The activities of these novel chiral 1,4-aminoalcoho...
Citation Formats
O. Büyükçakır, “Novel molecular building blocks based on bodipy chromophore: applications in metallosupramolecular polymers and ion sensing,” M.S. - Master of Science, Middle East Technical University, 2008.