Flexible Zirconium MOFs as Bromine‐Nanocontainers for Bromination Reactions under Ambient Conditions

Abstract

A series of flexible MOFs (PCN-605, PCN-606, and PCN-700) are synthesized and applied to reversible bromine encapsulation and release. The chemical stability of these Zr-MOFs ensures the framework's integrity during the bromine adsorption, while the framework's flexibility allows for structural adaptation upon bromine uptake to afford stronger host-guest interactions and therefore higher bromine adsorption capacities. The flexible MOFs act as bromine-nanocontainers which elongate the storage time of volatile halides under ambient conditions. Furthermore, the bromine pre-adsorbed flexible MOFs can be used as generic bromine sources for bromination reactions giving improved yields and selectivities under ambient conditions when compared with liquid bromine.

Reversible Release and Fixation of Bromine in Vacancy‐Ordered Bromide Perovskites

“…Considering the structural stability under the corrosive bromine and specific request for chemical interaction, only a few materials can be used for bromine chemisorption, including Co 2 Cl 2 BTDD [28] and Zr-MOFs (i.e., PCN-605, À606 and À700, arising from the host-guest interactions). [29] More or less, the complex organic ligand would make the materials preparation burdensome. Thus, the material research for bromine chemisorption is still in its infancy.…”

New functionalized MIL-53(In) solids: syntheses, characterization, sorption, and structural flexibility

“…The exible or dynamic MOFs (metal-organic frameworks), which were designed as '3rd generation porous coordination compounds' by Kitagawa, 1 have continuously attracted signicant attention due to the scientic interest in nding novel phenomena and their potential applications. [2][3][4][5][6] Among the large variety, in terms of chemical compositions and structural topologies of MOFs, the exible MIL-53(M)-type materials (where M ¼ Cr, Al, Fe, Ga, In, Sc) [7][8][9][10][11][12][13][14][15][16] manifest unprecedented large breathing effects in relation to their exible diamondshaped scaffolds (Fig. 1).…”

Zirconium metal–organic frameworks incorporating tetrathiafulvalene linkers: robust and redox-active matrices for in situ confinement of metal nanoparticles

“…It crystalizes in the orthorhombic space group Cmmm, similar to the structures of previously reported NU-901 57 and PCN-606. 58 The Zr 6 cluster in compound 1 is 8-connected ( Fig. 1b), therefore the overall structure can be simplied into a 4,8-connected net with scu topology ( Fig.…”