A successive layer-by-layer assembly of supramolecular frameworks driven by a novel type of face-to-face π+–π+ interactions
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Abstract
The solid-state complex [PTPH3](NO3)3·2(HNO3) (1) has been synthesized and characterized by X-ray studies, where PTPH3 is the triply protonated form of 4′-(4-pyridyl)-2,2′:6′,2′′-terpyridine (PTP). The solid-state structure of the complex reveals that the π+–π+ interactions are the major driving force in the crystal packing while π+–π, π–π and π–anion interactions assist the overall stabilization of self-assembly. Complex 1 exhibits two different π-stack layers, where layer 1 is generated through π+–π+ interactions and the mutual forces of π+–π+ and π+–π form layer 2. The interaction energies of the main driving forces (π+–π+, π+–π and π–anion interactions) observed in the crystal structure have been calculated using dispersion-corrected density functional theory (DFT-D). An analysis of the Hirshfeld surface of complex 1 shows the intermolecular interactions involved within the crystal structure and corresponding quantitative information are presented by fingerprint plots.
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