Wavelength‐Dependent Photochromic Inorganic–Organic Hybrid Based on a 3D Iodoplumbate Open‐Framework Material

Abstract

Organically templated inorganic open-framework materials have been fueled by intriguing architectures and topologies as well as fascinating physical properties. [1,2] These materials can be structurally classified into two subclasses: [1,3] the zeotype materials, in which all polyhedra of the wall are exclusively tetrahedral, and the frameworks built from mixed polyhedra.However, 3D open-framework materials constructed from purely octahedral units have not been obtained so far for these materials, although these have been observed in a few metal-organic frameworks [4] and purely inorganic materials. [5,6] Photochromic materials have received considerable attention for their potential applications in information display devices, high-density memory, and other high-tech areas. While purely organic [7] or inorganic [8] photochromic materials have been known for a long time, much attention has recently been dedicated to the development of photochromic inorganic-organic hybrids because of the novel and intriguing properties arising from the interactions between both organic and inorganic components. Structurally well-defined hybrids will give us better insight into these interactions. However, few hybrids based on transition-metal oxides and polyoxometalates have been explored with simultaneous characterization of their structure and photochromism.[9] Less attention has been paid to the photochromic hybrids based on metal halide semiconductors, [10] although the charge transfer between organic and inorganic components has been observed in these systems. [11] We obtained a yellow prismatic hybrid crystal (EDAMP) 2n (Pb 7 I 18 ) n ·4 n H 2 O (1; EDAMP = Et 2 NHC 6 H 4 -CH 2 C 6 H 4 NHEt 2 ) through a synchronous process of in situ N-alkylation and assembly under solvothermal conditions. This material represents a new subclass of 3D inorganic openframework materials built from purely octahedral units and behaves as a quantum-wire array. More interestingly, the compound shows interesting wavelength-dependent photochromism. The structure of the same single crystal was characterized before (1, yellow) and after visible irradiation (l = 550 nm; 2, olive green), as well as after further UV irradiation (l = 300 nm, 3, dark green).In traditional organic syntheses, N-alkylated products are obtained from the reaction of organic amines and alkyl iodides under alkaline conditions, whereas alkyl iodides are obtained from alcohols activated by HI under acidic conditions. We demonstrate herein a new one-step approach to form N-alkylated products (i.e. the alkylated DAMP compound in 1) through in situ N-alkylation of organic amines and alcohols under acidic conditions by using a solvothermal technique. The existence of alkylated DAMP compound in 1 has been proved by 1 H NMR and ESI-MS spectra (see the Supporting Information). This synchronous process can be expanded and a series of metal iodide hybrid frameworks can be realized by control of the alcohols (C1-C4), amines (aliphatic and aromatic), and metal salts (Pb, Bi, Sn). As for the...

Photoinduced Nonlinear Contraction Behavior in Metal–Organic Frameworks

“…[19] To further test our hypothesis, wavelength-dependenti rradiation experiments were carried out in the solid state. [20] Blue-violet light (420 nm) was used to irradiate Zn 2 -1 at 293 Kf or 10 min and gave rise to at wo-fold interpenetrated 3D MOF,[ Zn 2 (bdc) 2 (rctttcdp)] (denoted as Zn 2 -2 a), through as ingle-crystal-to-singlecrystal (SCSC) transformation ( Figure 3d;F igures S18 andS 19, Supporting Information). [21] This conversion,i nvolving a[ 2 + +2] photodimerization of pairs of 3-CH 3 -spy ligands, was confirmed by powder X-ray diffraction patterns and 1 Ha nd 13 CNMR spectra ( Figures S6 and S7;F igures S20a nd S21, Supporting Information).…”

1-Aminopyridinium triiodidoplumbate(II)

“…For background to hybrid materials, see: Rogow et al (2010); Thirumurugan & Rao (2008). For structures with lead halide building blocks, see: Li et al (2008); Zhang et al (2008).…”

“…E66, m1259 Inorganic metal-halide building-blocks have received special attention with respect to the construction of inorganicorganic hybrid materials (Rogow et al, 2010;Thirumurugan et al, 2008). Among these materials octahedral building blocks of lead halides are frequently found and numerous crystal structures, from one-dimensional chains to threedimensional frameworks (Li et al, 2008;Zhang et al, 2008), were observed. Herein we report the crystal structure of the title compound, (C 5 H 7 N 2 )[PbI 3 ] (I).…”

Structurally dependent thermochromism of two iodoargentate hybrids based on the intermolecular charge transfer

“…Recently reported thermochromic iodoplumbates [7e10] and iodobismuthates [11,12] as well as photochromic chlorobismuthates [13e16] and iodoplumbates [17] exhibit interesting component-structure-property relationship. Comparatively, chromism based on organicinorganic iodoargentate hybrids is rarely reported [18,19].…”