A new class of mesostructured metal germanium sulfide materials has been prepared and characterized. The synthesis, via supramolecular assembly of well-defined germanium sulfide anionic cluster precursors and transition-metal cations in formamide, represents a new strategy for the formation of this class of solids. A variety of techniques were employed to examine the structure and composition of the materials. Structurally, the material is best described as a periodic mesostructured metal sulfide-based coordination framework akin to periodic hexagonal mesoporous silica, MCM-41. At the molecular scale, the materials strongly resemble microstructured metal germanium sulfides, in which the structure of the [Ge 4 S 10 ] 4-cluster building-blocks are intact and linked via µ-S-M-S bonds. Evidence for a metal-metal bond in mesostructured Cu/Ge 4 S 10 is also provided.

We outline two methodologies to selectively characterize the Brønsted acidity of the external surface of FAU‐type zeolites by IR and NMR spectroscopy of adsorbed basic probe molecules. The challenge and goal are to develop reliable and quantitative IR and NMR methodologies to investigate the accessibility of acidic sites in the large pore FAU‐type zeolite Y and its mesoporous derivatives often referred to as ultra‐stable Y (USY). The accessibility of their Brønsted acid sites to probe molecules (n‐alkylamines, n‐alkylpyridines, n‐alkylphosphine‐ and phenylphosphine‐oxides) of different molecular sizes is quantitatively monitored either by IR or 31P NMR spectroscopy. It is now possible, for the first time to quantitatively discriminate between the Brønsted acidity located in the microporosity and on the external surface of large pore zeolites. For instance, the number of external acid sites on a Y (LZY‐64) zeolite represents 2 % of its total acid sites while that of a USY (CBV760) represents 4 % while the latter has a much lower framework Si/Al ratio.

Synthetic methods have been developed which yield large single crystals and highly crystalline phase-pure microporous layered SnS-n materials. This allows study of the structure-property-function relations of these materials. The tin sulfide layer of the SnS-1 structure type contains hexagonally shaped 24-atom rings which are constituted by six Sn 3 S 4 broken-cube cluster building units, linked together by double bridge Sn(m-S) 2 Sn sulfur bonds. The SnS-3 structure type contains elliptically shaped 32-atom rings which are also constructed from six Sn 3 S 4 broken-cube clusters. However, they are linked by double bridge Sn(m-S) 2 Sn sulfur bonds as well as tetrahedral edge-bridging Sn(m-S 2 SnS 2 )Sn spacer units. The SnS-1 structure type [A 2 Sn 3 S 7 ] was obtained in the presence of A+=Et 4 N+, DABCOH+ (protonated 1,8-diazabicyclooctane), and a mixed template system of NH 4 +/Et 4 N+, while the SnS-3 structure type [A 2 Sn 4 S 9] emerged in the presence of A+=Prn 4 N+ and Bun 4 N+. Various SnS-1 and SnS-3 structures are examined and compared in relation to the size/shape of constituent template cations. A particular kind of structure-directing function was observed, that is, larger template molecules create larger void spaces within and between the tin sulfide sheets. Unique framework flexibility was discovered for both structure types. In order to accommodate the size/shape changes of templates, the flexible porous tin() sulfide layers are able to undergo a certain degree of elastic deformation to alter the architecture of void spaces within and between the layers, rather than forming a completely new porous structure type. This is believed to be responsible for the relatively small number of structure types so far discovered for tin() sulfide-based microporous layered materials compared to the myriad of three-dimensional open-framework structure types found for the zeolites and aluminophosphates. The observed differences among the various SnS-1 or SnS-3 structures is significant and has resulted in distinct adsorption behavior towards guest molecules. The TPA-SnS-3 framework is also found to be pressure sensitive. This all bodes well for envisaged chemical sensor applications for this class of porous materials. rials, denoted R-SnS-n, where R represents the occluded

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