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Structural Diversity in Multinuclear Pd II Assemblies that Show Low‐Humidity Proton Conduction
Author(s) -
Samanta Dipak,
Mukherjee Partha Sarathi
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201305075
Subject(s) - proton , relative humidity , molecule , acceptor , conductivity , humidity , electrolyte , chemistry , crystallography , adsorption , thermal conduction , chemical physics , materials science , thermodynamics , composite material , physics , organic chemistry , condensed matter physics , electrode , quantum mechanics
Systematic investigation on synergetic effects of geometry, length, denticity, and asymmetry of donors was performed through the formation of a series of uncommon Pd II aggregates by employing the donor in a multicomponent self‐assembly of a cis ‐blocked 90° Pd II acceptor and a tetratopic donor. Some of these assemblies represent the first examples of these types of structures, and their formation is not anticipated by only taking the geometry of the donor and the acceptor building units into account. Analysis of the crystal packing of the X‐ray structure revealed several H bonds between the counteranions (NO 3 − ) and water molecules (OH⋅⋅⋅ON). Moreover, H‐bonded 3D‐networks of water are present in the molecular pockets, which show water‐adsorption properties with some variation in water affinity. Interestingly, these complexes exhibit proton conductivity (1.87×10 −5 –6.52×10 −4 Scm −1 ) at 296 K and low relative humidity (ca. 46 %) with activation energies of 0.29–0.46 eV. Moreover, the conductivities further increase with the enhancement of humidity. The ability of these assemblies to exhibit proton‐conducting properties under low‐humidity conditions makes these materials highly appealing as electrolytes in batteries and in fuel‐cell applications.