A two‐dimensional CdII coordination polymer based on naphthalenediimide: synthesis, crystal structure and photochromic properties

2018 
Naphthalenedi­imides, a class of organic dyes with an expanded π-electron-deficient plane, have attracted considerable inter­est because of their photo­induced electron transfer from neutral organic moieties to stable anionic radicals. This makes them excellent candidates for organic linkers in the construction of photochromic coordination polymers. Such a photochromic two-dimensional coordination polymer has been prepared using N,N′-bis­(pyridin-4-ylmeth­yl)naphthalene-1,8:4,5-bis(dicarboximide) (DPMNI). In crystallization tubes, upon slow diffusion of an MeOH solution of cadmium perchlorate into a CHCl3 solution of DPMNI, the complex poly[[bis­[μ2-2,7-bis­(pyridin-4-ylmeth­yl)benzo[imn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetrone-κ2N:N′]bis­(perchlorato-κO)cadmium(II)] chloro­form tetra­solvate], {[Cd(C26H16N4O4)2(ClO4)2]·4CHCl3}n, (I), was obtained. The asymmetric unit contains one Cd2+ cation, two DPMNI ligands, two coordinated ClO4− anions and four CHCl3 solvent mol­ecules. Each Cd2+ cation is inter­connected by four DPMNI linkers to generate a neutral two-dimensional naphthalenedi­imide coordination network with all the ClO4− anions above or below this plane. Strong inter­laminar anion–π inter­actions between the coordinated ClO4− anions and the imide rings of an adjacent layer lead to a three-dimensional supra­molecular structure. Compound (I) exhibits reversible photochromic behaviour and photocontrolled tunable luminescence properties, which may originate from the photoinduced electron-transfer generation of radicals in the DPMNI ligand.
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