Offene Gerüststrukturen von Übergangsmetallen

Abstract

In den letzten Jahren hat sich gezeigt, dass neben anorganischen Silicaten und Phosphaten auch Carboxylate, Arsenate, Sulfate, Selenate, Selenite, Germanate und Phosphite offene Gerüststrukturen bilden können. Von besonderem Interesse sind die organisch‐anorganischen Hybridverbindungen, die sich aus der Kombination der reichen Koordinationschemie der zentralen Metall‐Ionen vieler dieser Strukturtypen mit der Flexibilität und der Funktionalität organischer Verbindungsglieder (“Linker”) ergeben. Vor allem die Übergangsmetalle scheinen besonders viele Varianten zu liefern, was in den bevorzugten Koordinationsweisen, Ligandengeometrien und Valenzzuständen begründet ist. Außerdem lässt die Kombination der magnetischen Eigenschaften von Übergangsmetallen mit den Kanalstrukturen offener Gerüste interessante Anwendungen erwarten. In diesem Aufsatz werden die Synthesen, Strukturen und Eigenschaften einer Reihe von Übergangsmetallverbindungen mit offenem Gerüst vorgestellt.

Unprecedented Zeolite-Like Framework Topology Constructed from Cages with 3-Rings in a Barium Oxonitridophosphate

“…31 P triplequantum coherences, which are expected for the crystalline title compound, are only observed between peaks A and B, while the broad contributions centered around À3 and À9 ppm are reduced in intensity. It is noteworthy that the triple-quantum coherences involving phosphorus atoms P(1) and P (2) are not related to the broad features. Hence, the description of the sample as a heterogeneous mixture of the title compound and an amorphous impurity is consistent with the triple-quantum filtered 2D correlation spectrum (Figure 6).…”

“…ÀIII [2] ] h {3[3 8 4 6 8 12 ]} p {3[3 8 8 6 ]AE100ae(8-ring)}(Fm3c), the tetrahedra build up 3-, 4-, and 8-rings forming 3 8 4 6 8 12 cages that exhibit a CBU (Figure 9) that is not included in the current pool of CBU types so far. 41 The idealized solid body corresponds to the RCSR symbol rdo-a.…”

“…In addition to diverse metal phosphates, germanates, and borates, there are sulfates, arsenates, or phosphonates as well as organicÀinorganic hybrid compounds with porous networks. 1,2 However, many microporous structures are thermally and chemically not sufficiently stable to make their way toward advanced materials. Consequently, it is worthwhile to synthesize novel open-framework materials that exhibit three-dimensional, rigid framework structures based on vertex-sharing tetrahedra.…”

“…The fluoride route 4 has been utilized, and other tetrahedra centers (e.g., B, Ga, Zn) were included, resulting in new zeotypes in compound classes like silicoaluminophosphates (SAPOs) and metal-containing versions (e.g., MeAPO, MeAPSO) thereof. 2,5 Thus, the field of zeolite chemistry seems quite mature which means that the search for new framework types becomes increasingly challenging.…”

Water Stable Zr–Benzenedicarboxylate Metal–Organic Frameworks as Photocatalysts for Hydrogen Generation

“…[1][2][3][4][5][6][7][8] MOFs are crystalline solids in where metal ions or metal clusters are linked to multi-topical organic linkers forming an extended three-dimensional structure. [2,4,9,10] Some of the structures described for MOFs are isoreticular with zeolites and crystalline aluminophosphates, but MOFs surpass the properties of zeolites in terms of porosity and low framework density. Recently, we have been exploring [11][12][13] the possibility of using MOFs as semiconductors in where photon absorption produces a state of charge separation with a positive hole in the valence band and an electron in the conduction band.…”