Abstract
The growths, structures, phase transition temperatures, and molecular dynamics of mixed (MA)2Zn1-xCuxCl4 (x=0, 0.3, 0.5, 0.7, and 1) crystals were investigated to understand the effect of the random presence of paramagnetic Cu2+. In addition, the spin-lattice relaxation time T1ρ in the rotating frame by the magic angle spinning nuclear magnetic resonance (MAS NMR) method was obtained for 1H and 13C nuclei to understand the molecular dynamics for varying amounts of Cu2+ ions. The structure and phase transition temperature for the case where x=0.3 was similar to those for x=0, whereas those of x=0.5 and 0.7 were similar to those for x=1. Although the crystal structures and phase transition temperatures were similar for x (=0 and 0.3), and x (=0.5, 0.7, and 1), the molecular motions of 1H and 13C for x=0.3 differed from those for x=0, 0.5, 0.7, and 1. We compared the activation energies Ea by the molecular motions for 1H and 13C, based on the T1ρ. The Cu2+ presence for x=0.3 in the mixed structure indicates any differences in the Ea for 1H and 13C, and the replacement of Zn2+ ions by Cu2+ ions for x=0.3 was strongly affected by the molecular motions.
Highlights
Organic–inorganic hybrid compounds can combine the properties of organic and inorganic materials on the molecular level.1–3 Hybrid materials are very diverse and offer a broad range of structures, properties, and potential applications.4–9 Organic–inorganic hybrid compounds based on the perovskite structures are interesting materials owing to their potential for solar cells.10,11 toxicity and chemical instability problems of halide perovskites remain as the main disadvantages for their use in solar cells
The structures of the (MA)2Zn1-xCuxCl4 (x=0, 0.3, 0.5, 0.7, and 1) crystals were determined by X-ray diffraction (XRD) results at room temperature
The growths, structures, and phase transition temperatures of mixed (MA)2Zn1-x CuxCl4 (x=0, 0.3, 0.5, 0.7, and 1) crystals were investigated to understand the effect of the random presence of paramagnetic Cu2+ ions with a similar size
Summary
Organic–inorganic hybrid compounds can combine the properties of organic and inorganic materials on the molecular level. Hybrid materials are very diverse and offer a broad range of structures, properties, and potential applications. Organic–inorganic hybrid compounds based on the perovskite structures are interesting materials owing to their potential for solar cells. toxicity and chemical instability problems of halide perovskites remain as the main disadvantages for their use in solar cells. Organic–inorganic hybrid compounds can combine the properties of organic and inorganic materials on the molecular level.. Hybrid materials are very diverse and offer a broad range of structures, properties, and potential applications.. Organic–inorganic hybrid compounds based on the perovskite structures are interesting materials owing to their potential for solar cells.. Toxicity and chemical instability problems of halide perovskites remain as the main disadvantages for their use in solar cells. The structure of (CnH2n+1NH3)2MCl4 compounds, where n is an integer greater than zero and M represents a divalent metal (59Co, 64Cu, 65Zn, 113Cd, etc.), can be presented as an order of alternating organic–inorganic layers. The NH3+ polar heads of the chains are linked to the Cl– ions of the MCl6 octahedra by hydrogen bonds N–H⋯Cl. The organic chains are bounded by weak hydrogen bonds from the NH3+ groups to the Cl– ions. In the abbreviation used here, the first two letters represent the organic ions (MA=methyl ammonium)
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