A series of trivalent lanthanides (Sm, Eu, Gd, Tb, Dy) have been complexed to the dianionic ligand, 4,4'-disulfo-2,2'-bipyridine-N,N'-dioxide, L, in a 3:1 ratio to form trianionic complex building blocks. These units were then cross-linked into a network solid by addition of BaCl2 to form mixed-metal networks of formula {Ba2(H2O)4[LnL3(H2O)2](H2O)nCl}infinity, Ln = Sm3+ (1), Eu3+ (2), Gd3+ (3), Tb3+ (4), Dy3+ (5). The networks were isostructural and contained open channels which readily absorbed and desorbed water accompanied by a spongelike shrinkage and expansion of the host. CO2 sorption measurements confirmed microporosity giving a DR surface area of 718 m2/gm and an average pore size of 6.4 A. Ligand L sensitized all the lanthanide ions with the exception of Gd3+. Studying the series of Ln complexes allowed the determination of the triplet state energy of L which is itself a new ligand for sensitization purposes. The luminescent properties of the lanthanide building blocks were retained in the porous network solid. From the luminescence data, it was possible to attribute the spongelike properties of the network to the Ba2+ coordination sphere rather than the Ln3+ center. Networks were characterized by X-ray crystallography, PXRD, DSC/TGA, water vapor and gas sorption, and luminescence spectroscopy.

Metal-organic frameworks have demonstrated functionality stemming from both robustness and pliancy and as such, offer promise for a broad range of new materials. The flexible aspect of some of these solids is intriguing for so-called 'smart' materials in that they could structurally respond to an external stimulus. Herein, we present an open-channel metal-organic framework that, on dehydration, shifts structure to form closed pores in the solid. This occurs through multiple single-crystal-to-single-crystal transformations such that snapshots of the mechanism of solid-state conversion can be obtained. Notably, the gas composing the atmosphere during dehydration becomes trapped in the closed pores. On rehydration, the pores open to release the trapped gas. Thus, this new material represents a thermally robust and porous material that is also capable of dynamically capturing and releasing gas in a controlled manner.

Lewis acidic, chelating diborane 1 forms stable oxonium acids 2 in the presence of excess MeOH or water. Diborane 1 is shown to be an effective co-initiator for the suspension polymerization of isobutene in aqueous media at sufficiently low temperatures. Poly(isobutene) or butyl rubber is obtained at moderate to high conversion and with Mw < 200 K and PDI approximately 2 under these conditions.

A series of permanently porous luminescent lanthanide frameworks of the general formula, [Na 6 (H 2 O) 6 ]-[Ln(L) 4 ](H 2 O) n Cl, Ln ) Sm (1), Eu (2), Gd (3), Tb (4), and Dy (5), have been prepared by the reaction of trivalent lanthanide salts with sodium-4,4′-disulfo-2,2′-bipyridine-N,N′-dioxide, L. The structures are formed via the one-pot self-assembly of the anionic cubic metalloligand, [Ln(L) 4 ] 5-, and subsequent cross-linking with sodium cations and chloride to afford a three-dimensional network with two-dimensional channels. The cross-linking units involve [Na 4 Cl] 3+ clusters which resemble ideal faces of the halite structure. Both coordinated and uncoordinated water molecules, up to ∼80%, can be reversibly removed from 1-5 as identified using thermal gravimetric analysis/differential scanning calorimetry (TGA/DSC) leaving a rigid and porous framework with a Dubinin-Radushkevich (DR) surface area of 426 m 2 /g determined using CO 2 adsorption. The permanent microporosity of the framework is also supported by the energy level splitting in the luminescence spectra which are maintained in both the hydrated and mostly dehydrated frameworks. Compounds 1-5 were each characterized by X-ray crystallography, TGA/ DSC, water and CO 2 sorption analyses, and luminescence spectroscopy.