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Metal-organic frameworks (MOFs) are promising porous materials for gas separation and storage as well as sensing. In particular, a series of isostructural MOFs with coordinately unsaturated metal centers, namely, CPO-27-M or M-MOF-74 (M = Mg, Zn, Mn, Fe, Ni, Co, Cu), have shown exceptional adsorption capacity and selectivity compared to those of classical MOFs that contain only fully coordinated metal sites. Although it is widely accepted that the interaction between guest molecules and exposed metal centers is responsible for good selectivity and large maximum uptake, the investigation of such guest-metal interaction is very challenging because adsorbed molecules are usually disordered in the pores and undergo rapid thermal motions. 2H solid-state NMR (SSNMR) spectroscopy is one of the most extensively used techniques for capturing guest dynamics in porous materials. In this work, variable-temperature 2H wide-line SSNMR experiments were performed on CPO-27-M (M = Mg, Zn) loaded with four prototypical guest molecules: D2O, CD3CN, acetone-d6, and C6D6. The results indicate that different guest molecules possess distinct dynamic behaviors inside the channel of CPO-27-M. For a given guest molecule, its dynamic behavior also depends on the nature of the metal centers. The binding strength of guest molecules is discussed on the basis of the 2H SSNMR data. [ABSTRACT FROM AUTHOR]

The synthesis of germanium nanocrystals (GeNCs) with well-defined surface chemistry is of considerable interest because of their potential applications in the optoelectronic, battery, and semiconductor industries. Modifying and tailoring GeNC surface chemistry provides an avenue by which reactivity, environmental compatibility (e.g., solubility, resistance to oxidation), and electronic properties may be tailored. Hydride-terminated GeNCs (H-GeNCs) are of particular interest because the reactivity of surface Ge-H bonds toward alkenes and alkynes via hydrogermylation affords the potential for convenient modification; however, these reactions and their scope have not been widely explored. This report describes a straightforward route for preparing a GeNC/GeO2 composite via disproportionation of heretofore-unexplored Ge(II) oxide-based precursor from which the H-GeNCs were freed by subsequently chemical etching. The H-GeNCs were derivatized using a series of hydrogermylation approaches (i.e., thermally activated, radical-initiated, and borane-catalyzed). The presented findings indicate surface functionalization occurs under all conditions investigated; however the nature of surface species (i.e., monolayers vs multilayers) and surface coverage varies depending upon the conditions employed. [ABSTRACT FROM AUTHOR]

The synthesis of germanium nanocrystals (GeNCs) with well-defined surface chemistry is of considerable interest because of their potential applications in the optoelectronic, battery, and semiconductor industries. Modifying and tailoring GeNC surface chemistry provides an avenue by which reactivity, environmental compatibility (e.g., solubility, resistance to oxidation), and electronic properties may be tailored. Hydride-terminated GeNCs (H-GeNCs) are of particular interest because the reactivity of surface Ge-H bonds toward alkenes and alkynes via hydrogermylation affords the potential for convenient modification; however, these reactions and their scope have not been widely explored. This report describes a straightforward route for preparing a GeNC/GeO 2 composite via disproportionation of heretofore-unexplored Ge(II) oxide-based precursor from which the H-GeNCs were freed by subsequently chemical etching. The H-GeNCs were derivatized using a series of hydrogermylation approaches (i.e., thermally activated, radical-initiated, and borane-catalyzed). The presented findings indicate surface functionalization occurs under all conditions investigated; however the nature of surface species (i.e., monolayers vs multilayers) and surface coverage varies depending upon the conditions employed.

Metal-organic frameworks (MOFs) are promising porous materials for gas separation and storage as well as sensing. In particular, a series of isostructural MOFs with coordinately unsaturated metal centers, namely, CPO-27-M or M-MOF-74 (M = Mg, Zn, Mn, Fe, Ni, Co, Cu), have shown exceptional adsorption capacity and selectivity compared to those of classical MOFs that contain only fully coordinated metal sites. Although it is widely accepted that the interaction between guest molecules and exposed metal centers is responsible for good selectivity and large maximum uptake, the investigation of such guest-metal interaction is very challenging because adsorbed molecules are usually disordered in the pores and undergo rapid thermal motions. (2)H solid-state NMR (SSNMR) spectroscopy is one of the most extensively used techniques for capturing guest dynamics in porous materials. In this work, variable-temperature (2)H wide-line SSNMR experiments were performed on CPO-27-M (M = Mg, Zn) loaded with four prototypical guest molecules: D2O, CD3CN, acetone-d6, and C6D6. The results indicate that different guest molecules possess distinct dynamic behaviors inside the channel of CPO-27-M. For a given guest molecule, its dynamic behavior also depends on the nature of the metal centers. The binding strength of guest molecules is discussed on the basis of the (2)H SSNMR data.