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Cyanine dyes play an indispensable and central role in modern fluorescence-based biological techniques. Despite their importance and widespread use, the current synthesis methods of heptamethine chain modification are restricted to coupling reactions and nucleophilic substitution at the meso position in the chain. Herein, we report the direct transformation of Zincke salts to cyanine dyes under mild conditions, accompanied by the incorporation of a substituted pyridine residue into the heptamethine scaffold. This work represents the first general approach that allows the introduction of diverse substituents and different substitution patterns at the C3'-C5' positions of the chain. High yields, functional tolerance, versatility toward the condensation partners, and scalability make this method a powerful tool for accessing a new generation of cyanine derivatives.
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http://dx.doi.org/10.1021/jacs.9b02537 | DOI Listing |
J Mol Liq
October 2025
Chemical Processes and Materials Research Group, School of Engineering, Just Transitions Lab, Centre for Energy Transition, University of Aberdeen, King's College, Old Aberdeen AB24 3UE, UK.
We report the synthesis, characterization, and conductivity response of five new dicationic ionic liquid (DCIL) salts featuring phenyl-extended viologen cores coupled with terminal oxyethylene groups (CHCHO) of two different lengths ( = 3 and 7) and paired with three distinct counter-anions: fluorosulfonylimide ((N(FSO) , FSI), trifluoromethylsulfonylimide (N(CFSO) , TFSI), and nonaflate (CF(CF)SO , ONf). All salts are amorphous and exhibit near- or sub-zero glass transition temperatures ( ), attributed to the plasticizing effect of the (CHCHO) chains, and show chromophore responses in organic solvents. The five salts display large dielectric responses with conductivities in the 10 S·cm range, facilitated by the smaller counter-anion, FSI.
View Article and Find Full Text PDFSelective skeletal and peripheral editing of the pyridine moiety has broadly expanded the chemical space. While C-H functionalization at C2 and C4 positions are enabled by the inherent reactivity of this heteroarene, selective derivatization at the C3 position has long posed a significant challenge. Recently, based on a dearomatization-rearomatization sequence, involving Zincke imine intermediates, selective halogenation (-Br, -Cl, and -I) and isotopic labelling were accomplished.
View Article and Find Full Text PDFInorg Chem
February 2025
Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States.
Chiral organic-inorganic metal halide (OIMH) materials are gaining increasing attention as candidates for asymmetric materials due to their unique photoelectric, chiral optic, and spintronic properties. The introduction of chirality into OIMHs is usually achieved by the use of chiral organic cations, while previous studies often focus on primary ammonium cations derived from commercially available chiral amines, limiting the tunability of the OIMH materials. Herein, we report the use of Zincke reactions to synthesize chiral N-substituted pyridinium salts, namely, (R)/(S)-methylbenzylpyridinium (/-MBnP) chloride and the corresponding 1D chiral OIMHs, (/-MBnP)PbX3 (X = Cl, Br, and I).
View Article and Find Full Text PDFChemistry
March 2025
Department of Chemistry, University of Liverpool, Liverpool, L69 7ZD, UK.
The Zincke reaction and Birch reduction have been one of the few reactions that allow for ring opening of pyridines ever since the discovery of pyridine more than a century ago. This paper presents a new addition to the list of pyridine ring-opening reactions, reductive Zincke reaction, which affords saturated δ-amino ketones. Under the catalysis of a simple rhodium complex, pyridinium salts with diverse substituents are reduced with formic acid, ring-opened with water, transaminated with a secondary amine and further reduced to afford a wide range of δ-amino ketones, including those in which the alkane chain of the ketones is selectively deuterated or fluorinated.
View Article and Find Full Text PDFJ Org Chem
September 2024
Department of Chemistry, Temple University, 1901 North 13th Street, Philadelphia, Pennsylvania 19122, United States.