ABSTRACT
Treatment of Na3[Au3Co2(d-pen)6] (Na3[1]; d-H2pen = d-penicillamine) with M(OAc)2 (M = NiII, MnII) in water gave ionic crystals of [M(H2O)6]3[1]2 (2M) in which [1]3- anions are hydrogen-bonded with [M(H2O)6]2+ cations to form a 3D porous framework with a porosity of ca. 80%. Soaking crystals of 2Ni in its mother liquor afforded crystals of [Ni(H2O)6]2[{Ni(H2O)4}(1)2] (3Ni) in which [1]3- anions are connected to trans-[Ni(H2O)4]2+ and [Ni(H2O)6]2+ cations through coordination and hydrogen bonds, respectively, to form a 1D porous framework with a porosity ca. 60%. Further soaking crystals led to [{Ni(H2O)4}3(1)2] (4Ni), in which [1]3- anions are connected to cis-[Ni(H2O)4]2+ and trans-[Ni(H2O)4]2+ cations through coordination bonds in a dense framework with a porosity of ca. 30%. A similar two-step crystal-to-crystal transformation mediated by solvent proceeded when crystals of 2Mn were soaked in a mother liquor. However, the transformation of 2Mn generated [{Mn(H2O)4}(H1)] (4'Mn) as the final product, in which [H1]2- anions are connected to cis-[Mn(H2O)4]2+ cations through coordination bonds in a very dense framework with a porosity ca. 5% by way of [Mn(H2O)6]2[{Mn(H2O)4}(1)2] (3Mn), which is isostructural with 3Ni. While all the compounds adsorbed H2O and CO2 depending on the degree of their porosity, unusually large NH3 adsorption capacities were observed for 4Ni and 4'Mn, which have dense frameworks.
ABSTRACT
Based on the mixed phthalate (phth2-) and adipate (ad2-), [Nd2(ad)(phth)2(H2O)4] (I) and [Ln(ad)0.5(phth)(H2O)2] (Ln = EuIII (II), GdIII (III), TbIII (IV), DyIII (V), ErIII (VI), TmIII (VII), 1EuIII:10TbIII (VIII), 3EuIII:10TbIII (IX), and 5EuIII:10TbIII (X)) were synthesized and characterized. Complexes VIII-X show excellent ratiometric temperature sensing behavior in physiological and higher temperature ranges (303-423 K) rendered by the TbIII-to-EuIII energy transfer process. The efficiency of the process as illustrated through the lifetime measurements depends on both the EuIII:TbIII mole ratio and the temperature. The performance of X in terms of relative sensitivity ( Sr), temperature resolution, and measurement repeatability were determined, revealing the maximum Sr ( Sm) of 1.21%·K-1 at 303 K with reliable temperature resolution and excellent repeatability.
ABSTRACT
Treatment of Λ-fac-[Co(d-pen-N,S)3]3- (d-H2pen = d-penicillamine) with Cu+ in water gave a stable CoCu complex, ΛΛ-[Co2Cu3(d-pen)6]3- ([1]3-), having three thiolato-copper(i)-thiolato moieties that bridge two cobalt(iii) centres. Complex [1]3- was isolated as a coordination polymer of Na3[1], which was converted to a complex salt of [Cr(H2O)6][1] by treatment with Cr(NO3)3.
ABSTRACT
A unique pH-controlled synthesis of two metallosupramolecular structures from CoAu complex anions and ZnII cations is reported. A dense coordination polymer (porosity â¼13%) was formed at a pH of 5.0, whereas a porous ionic framework (porosity â¼61%) that selectively adsorbs CO2 and H2O was created when the pH was adjusted to 5.5.
ABSTRACT
A unique example of a hydrogen-bonded ionic solid with a porosity of 80 %, [Co(H2O)6]3 [Co2Au3 (d-pen-N,S)6]2 (1; d-H2 pen=d-penicillamine), composed of [Co(H2O)6](2+) cations and [Co2Au3 (d-pen-N,S)6 ](3-) anions, is reported. Solid 1 was kinetically produced and was then transformed stepwise into two more thermodynamically stable solids with lower porosities, [Co(H2O)4 ][Co(H2O)6]2 [Co2Au3 (d-pen-N,S)6]2 (2) and [Co(H2O)4]3 [Co2 Au3 (d-pen-N,S)6]2 (3), through the coordination of the free carboxylate groups in [Co2Au3 (d-pen-N,S)6](3-) to Co(II) centers. Solids 1-3 were structurally characterized, and the selective adsorption of small molecules into their pores was investigated.
