Rational Construction of Porous Polymeric Cadmium Ferrocene-1,1′-disulfonates for Transition Metal Ion Exchange and Sorption

Abstract

Porous pillared bilayer open coordination polymer {[Cd(bpp) 2 (O 3 SFcSO 3 )] • (CH 3 OH) 2 • (H 2 O) 6 } n 1 (Fc ) ferrocene) and 3D porous coordination polymer {[Cd(bpy) 2 (O 3 SFcSO 3 )] • (CH 3 OH) 4 } n 2 have been assembled from Cd(NO 3 ) 2 , ferrocene-1,1′disulfonate, and bridging ligands 1,3-bis(4-pyridyl)propane (bpp) or 4,4′-bipyridine (bpy). Both of them show very special adsorption properties to copper salts. Along with the increase in the solution concentration of Cu(NO 3 ) 2 , the percentage of adsorbed copper ions falls, but the percentage of exchanged central cadmium ions and the amount of adsorbed copper ions rises. In dilute solution, there mainly exists metal ion sorption, whereas both ion sorption and exchange are in charge of the whole progress in strong solution. Meanwhile, such materials could be used as ideal metal ion adsorbent toward some other metal cations, including of Pb 2+ , Zn 2+ , Mn 2+ , Co 2+ , Ni 2+ . However, when all these metal ions coexist in a mixture solution, the two ferrocenyl complexes selectively adsorb large amounts of only Pb 2+ (for 1, 88.54%; for 2, 75.80%) and Cu 2+ (for 1, 90.94%; for 2, 79.45%). Ion sorption and central cadmium ion exchange might be considered as being dominated by the coordination ability of metal ions to free functional groups, ionic radii of adsorbed metal ions, and the solution concentration of adsorbed metal salts. On the basis of the recognition of ion exchange, the center metal ion-exchange product of 2, {[Cd 0.5 Cu 0.5 (bpy) 2 (O 3 SFcSO 3 )] • (CH 3 OH) 4 } n 3, could be obtained by ionexchange-induced single crystal to single crystal transformation.

Tunable structures aroused by cation exchange reaction of solvent-mediated mechanism

“…Our previous investigations [21][22][23][24][25] indicate that the ion exchange reaction mechanism can be classified into two kinds. One is solid-state diffusion mechanism [26,27] with a nonhomogeneous phase exchange process.…”

Crystal structure of catena-(μ2-4,4´-bipyridine)sil ver(I)hydrogen-bis-(5- nitro-1,2-carboxybenzene-3-carboxylato)tetrahydrate, [Ag(C10H8N2)]·(C18H9O16N2)·4H2O, C28H25AgN4O20

“…The design and construction of metal-organic coordination polymers has been shown to be apromising field, not only because of their potential applications as functional solid materials in ion exchange,catalysis,luminescence, magnets, nonlinear optics, and gass eparation/storage [1][2][3][4][5][6]…”

“…The design and construction of metal-organic coordination polymers has been shown to be apromising field, not only because of their potential applications as functional solid materials in ion exchange,catalysis,luminescence, magnets, nonlinear optics, and gass eparation/storage [1][2][3][4][5][6].A mong various organic ligands, rodlike N,N'-donor building blocks, such as the conventionally employed 4,4'-bipyridine (bipy),a re widely employed to construct such coordination polymers [3,[7][8][9][10][11]. [Ag(m 2 -bipy)] + complexes have been extensively studied in coordination chemistry [12][13][14][15].…”

A Hydroscopic Self‐Catenated Net Formed by Borromean Layers Interlocked by Ferrocenyl Bridging Ligands

“…[16] The complex exhibits a strong attachment to water molecules, because the partially dehydrated crystal of 1 can rehydrate spontaneously and rapidly in air to the nascent state with identical cell parameters to thos of the assynthesized 1. Further the amorphous sample of 1 can be regenerated by water to the crystalline material again.…”