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Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
Published on: May 28, 2014
Proton-conducting coordination polymers formed from bipyridine phosphonate ligands
Prajakta Mohan Ramteke1,2, Tomáš Plecháček3, Matouš Kloda1
1Institute of Inorganic Chemistry of the Czech Academy of Sciences, Husinec-Řež 1001, 25068 Řež, Czech Republic. hynek@iic.cas.cz.
Abstract:
Phosphonate-based linkers remain underexplored for constructing proton-conductive coordination polymers. We synthesized three new coordination polymers, ICR-25, ICR-26, and ICR-27, employing two new phosphonate ligands derived from 4,4'-bipyridine: 4,4'-bipyridine-2,2',6,6'-tetraphosphonic acid (H8BipyTP) and 4,4'-bipyridine-2,2'-diphosphonic acid (H4BipyDP), with Ca2+ (ICR-25), Al3+ (ICR-26), and Mg2+ (ICR-27) ions. These materials represent new members of the limited family of N-heteroaromatic phosphonate frameworks. ICR-25 and ICR-26 contain hydrophilic voids with bound water molecules, while ICR-27 is a nonporous layered structure. In the structure of ICR-25, there are numerous acidic -OH groups, while ICR-26 is characterized by the presence of uncoordinated N heteroatoms. The proton conductivities of ICR-25 and ICR-26 are measured at relative humidity values of 75% and 92%, yielding the maximum value of 2.0 × 10-4 S cm-1, which is achieved by ICR-26 at 92% humidity and a temperature of 306 K. Activation energies indicate the vehicle mechanism of proton transport in ICR-25 and the proton-hopping (Grotthuss) mechanism in the case of ICR-26. We thereby propose that using the N-heteroaromatic phosphonate ligands is an efficient method for the construction of proton-conducting coordination polymers.
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