Polymorphic layered copper phosphonates: exfoliation and proton conductivity studies.

Dalton Trans

State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210023, P. R. China.

Published: May 2019

Three polymorphic copper carboxylate-phosphonates are reported, namely, α-Cu(4-cnappH)(H2O) (α-Cu-1), α-Cu(4-cnappH)(H2O)·0.5H2O (α-Cu-2) and β-Cu(4-cnappH)(H2O) (β-Cu), where 4-cnappH3 is (4-carboxynaphthalen-1-yl)phosphonic acid. All show layer structures but with different layer topologies. The layer topologies of the α-phases are similar, where the distorted {CuO4} planes and {PO3C} tetrahedra are corner-shared forming an inorganic layer containing 8- and 16-member rings. In β-Cu, double chains made up of corner-sharing {CuO5} and {PO3C} are crossed-linked through edge-sharing of the {CuO5} square pyramids to form an inorganic layer containing 4- and 8-member rings. The uncoordinated carboxylate groups are protonated and are involved in the interlayer hydrogen bonds in all cases. Antiferromagnetic interactions are dominant in all cases. Compounds α-Cu-1, α-Cu-2 and β-Cu can be exfoliated in THF resulting in 2D nanosheets of mainly two-layer thickness. Proton conductivity measurements reveal that the proton conduction is more favorable in α-Cu-2 than in α-Cu-1, but exfoliation into nanosheets decreases the conductivity.

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Source
http://dx.doi.org/10.1039/c9dt00970aDOI Listing

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