Double-bridged Tetrathiafulvalene Macrocycles with m-Xylylene, Trimethylene, and Glucose Linkers: Synthesis and Characterization
The synthesis of novel tetrathiafulvalene (TTF) macrocycles with m-Xylylene, Trimethylene, and Glucose units is reported. The synthesis involves the preparation and stepwise base deprotection of cyanoethyl protected TTF, its reaction with m-xylyldibromide, 1,3-bromopropane, and/or acetylated dihaloglucose, followed by deacetylation.
The p-electron donor tetrathiafulvalene (TTF) is redox-active, exhibiting a reversible two-step oxidation. It has desirable characteristics that are exploited to give a variety of uses in molecular, supramolecular, and materials chemistry (Jeppensen et al. 2004; Iyoda et al. 2004; Rovira 2004). When incorporated in a macrocycle, this property can be utilized to influence the complexation of guest molecules. It can also act as a sensor where complexation of ions or molecules is detected by a change in redox property of the host (Jorgensen et al. 1994). Sugars, on the other hand, are polyhydroxylated and capable of forming multiple H-bonding interactions with the guest molecules in a macrocyclic system (Simmonds 1992). They may exhibit high stereospecificity because of the presence of several chiral centers. The macrocycles with TTF and sugar units have potential applications in chemical and pharmaceutical industries, and biological research. For example, they can be used as a valuable tool for drug delivery (Hansen et al. 1992). Molecular systems that are based on host-guest interaction have been synthesized and were found capable of acting as sensors, catalysts, and molecular switches (Jorgensen et al. 1994; Demiralp & Goddard 1997; Bryce et al. 1998; Jeppensen et al. 2000; Takimiya et al. 2000; Simonsen & Becher 1997; Simonsen et al.1999). Some of these TTF macrocycles are double-bridged type but none so far are with sugar units. In this paper, we describe the synthesis of novel macrocycles containing glucose units.
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