Layered Zinc Phosphates with Photoluminescence and Photochromism: Chemistry in Deep Eutectic Solvents

Abstract

A metal‐activator‐free orange phosphor was synthesized from ZnO/H3PO3/diamine in choline chloride/oxalic acid deep eutectic solvent, which also acted as methylating agent and source of ethylene glycol (EG) by dissociation of choline ions. Interlayer incorporation of a dimethylated amine made the resulting layered zinc phosphate (“ZnPO”, see picture) photochromic, and their interaction with EG formed fluorophores with orange photoluminescence.

A Room‐Temperature X‐ray‐Induced Photochromic Material for X‐ray Detection

“…Electron transfer has been found to be one of the subsequent photophysical processes in some reported X-rayinduced photochromic species. [3,4,[7][8][9][10] In this case, electron spin resonance (ESR) studies were carried out to make sure the presence of electron trans- fer during X-ray irradiation. The experimental results showed that compound 1-Y and its decolored samples are ESR silent but 1-HX-B and 1-SX-B display single line signals with g factors of 2.0029 and 1.9988, respectively ( Figure 5).…”

“…Types of electron transfer in known X-ray-induced photochromic species are ligand-to-metal charge transfer, [7, 9b] metal-to-metal charge transfer, [3] metal-centered transitions, [4] charge transfer between inorganic frameworks and organic templates, [8] and charge transfer between inorganic frameworks and doped metals. [10] In our case, the Br!L electron transfer is a key factor for the X-ray-induced photochromism of 1-Y.…”

“…Photochromic species generally show reversible color change upon external stimuli. [2] If X-rays behave as a stimulus, they are ideal candidates of such materials because they are recyclable.There have been some excellent studies on X-ray-induced photochromic materials, like Prussian blue analogs, [3] Fe II spin-crossover complexes, [4] manganite, [5] spinel, [6] cobalt dioxolene, [7] zinc phosphate with methylviologen cations, [8] BiOI/BiI-nylon11 composite films, [9] and oxometallates with impurities (such as LiNbO 3 :Cu), [10] in strict accordance with the definition of photochromism. [2] However, to the best of our knowledge, examples of X-ray-induced photochromic materials are still rather rare in the literature.…”

“…Even so, most of them only show X-ray-induced photochromism below room temperature, [3][4][5][6][7] which is not economic and convenient for use. Moreover, in the reported studies of X-ray-induced photochromic species, the adopted X-ray was either hard (l < 1 ) [3,4] or soft (l > 1 ), [5][6][7][8][9][10] but not both. Thus, it is desirable to develop new room-temperature X-ray-induced photochromic species which are susceptible to both hard and soft X-rays.Herein, we present a room-temperature X-ray-induced photochromic metal-organic complex, [ZnLBr 2 ] (…”

Two Zeolite‐Type Frameworks in One Metal–Organic Framework with Zn24@Zn104 Cube‐in‐Sodalite Architecture

“…This is the first example of two types of zeolite frameworks nested in the same material, and it also demonstrates a new mechanism for the formation of nested cage structure that is distinctly different from the previously reported mechanism based on polyfunctional ligands. [14][15][16] This new type of intercage linking mechanism through metal sites might be adapted for the synthesis of discrete coordination polyhedra as well, which may lead to the creation of sophisticated coordination assemblies, and perhaps a better understanding of selfassembly processes in both synthetic and natural systems. Received: May 3, 2012 Revised: June 5, 2012 Published online: July 12, 2012 .…”