Structural Arrangement of 4‐[4‐(Dimethylamino)phenylazo]pyridine Push–Pull Molecules in Acidic Layered Hosts Solved by Experimental and Calculation Methods

Abstract

4‐[4‐(dimethylamino)phenylazo]pyridine (further denoted as G) representing a type of push–pull molecules can be intercalated into α‐ and γ‐modifications of zirconium phosphate (α‐ZrP and γ‐ZrP) and into zirconium (4‐sulfophenyl)phosphonate (ZrSPP). The obtained intercalates form single phases with interlayer distances of 12.75, 16.31, and 24.11 Å for α‐ZrP·0.2G·1.5H2O, γ‐ZrP·0.2G·1.5H2O, and ZrSPP·0.5G·1H2O, respectively. The increase of the interlayer distance upon intercalation suggests that the molecules of the intercalated guest lie parallel to the host layers. All intercalates were further characterized by IR and UV/Vis spectroscopy. The arrangement of the guests in the interlayer space was determined by molecular simulation methods. The calculations were performed separately for protonated and unprotonated forms of the guest in the models of hydrated and dehydrated α‐ZrP and γ‐ZrP intercalates. In the case of the α‐ZrP intercalate, the presence of interlayer water stabilizes the head‐to‐tail arrangement of the guest molecules. Dehydration of this intercalate disturbs their arrangement, mainly in the case of protonated guest molecules. In the case of dehydrated γ‐ZrP, the guest molecules are head‐to‐tail ordered, and the guest molecules in the hydrated form of γ‐ZrP are more disordered than in the dehydrated intercalate. The simulations also describe a layer shift present in the dehydrated γ‐ZrP intercalate, which explains why the rehydration of this intercalate is not possible.

The Dipole Moment Inversion Effects in Self-Assembled Nanodielectrics for Organic Transistors

“…27−30 However, 191 the generation of diazonium salt by aqueous HBF 4 + NaNO 2 192 produces the N-asymmetric azabenzenes in high yields. 31 The 193 structure of 5 was confirmed by single-crystal diffraction (see 194 the Supporting Information). Surprisingly, functionalization of 195 5 with a diethyl-phosphonate group was unsuccessful via either 196 Pd-catalyzed Hirao or Ni-catalyzed coupling.…”

Revisiting the Old and Golden Inorganic Material, Zirconium Phosphate: Synthesis, Intercalation, Surface Functionalization, and Metal Ion Uptake

“…In this arena, cointercalation of a suitable donor and acceptor pair which involves donor-to-acceptor (D−A) energy transfer and intercalation of the donor−pi−acceptor (D−π−A) system which involves internal charge transfer (ICT) are the two most dominant modes of energy transfer within the ZrP gallery. 102,129,139 4.2.1. Donor-to-Acceptor Energy Transfer Inside Zirconium Phosphate Gallery.…”

“…Melanova et al investigated the structural arrangement of 4-[4-(N,N-dimethylamino) phenylazo]pyridine-based push− pull system into the gallery of αand γ-ZrP. 129 TGA and molecular simulations are consistent with parallel (head-to-tail) orientation of guest molecules inside the ZrP gallery for the generation of molecular dipoles. The same research group reported the first of its kind intercalation and ICT enhancement of tripodal tris[(pyridine-4-yl)-phenyl]amine (TPPA) push− pull system inside αand γ-ZrP.…”

“…Several extensions have been reported thus far to increase the overall efficiency of solar energy capture. In this arena, cointercalation of a suitable donor and acceptor pair which involves donor-to-acceptor (D–A) energy transfer and intercalation of the donor–pi–acceptor (D−π–A) system which involves internal charge transfer (ICT) are the two most dominant modes of energy transfer within the ZrP gallery. ,, …”

Simultaneous Detection of Cu2+ and Hg2+ via Two Mutually Independent Sensing Pathways of Biimidazole Push–Pull Dye

“…Herein we have designed a push–pull dye having 4,5-bis­[4-( N , N -dimethylamino)­phenyl]­imidazole as the donor moiety and 4,5-dicyanoimidazole as the acceptor unit (Figure c). The polarizability of such D−π–A system depends on the chemical structure, particularly on the electronic characteristics of the donor and acceptor moiety, overall geometry, and length of the π-conjugated linker . Thus, these compounds find tremendous applications as active parts of light-emitting diodes, optoelectronic devices, and organic photovoltaic cells, etc .…”