New Tricks for an Old Dog: The Carbonate Ion as a Building Block for Networks Including Examples of Composition [Cu₆(CO₃)₁₂{C(NH₂)₃}₈]⁴⁻ with the Sodalite Topology

Abstract

ZuschriftenIn einem anionischen Koordinationspolymer sind die Cu II -Ionen durch Carbonat-Ionen zu einem kubischen Netzwerk verknüpft, das die Topologie des im Hintergrund dargestellten Sodalithnetzes hat. Paare von Guanidinium-Ionen in den hexagonalen Fenstern des Sodalithkäfigs (nicht gezeigt) dienen als H-Brücken-Template, während Alkalimetallionen (grün) gut in die quadratischen Fenster passen. Näheres erläutern R. Robson et al. auf den folgenden Seiten.

Cubic, Hydrogen‐Bonded (10,3)‐a Networks in the Family [C(NH2)3][N(CH3)4][XO4] (X=S, Cr, and Mo)

“…Although numbers of metal/ligand-bonded frameworks with the (10,3)-a topology are now increasing, hydrogen-bonded examples such as the ones reported here remain rare. [11] The results presented here, together with others, [1,2] indicate the potential of the guanidinium cation as a Angewandte Chemie structure-directing ion for the generation of new networks of high symmetry. These are possibilities we are actively pursuing.…”

“…In an extensive family of carbonate-bridged coordination polymers reported recently, the guanidinum cation plays the crucial structural role represented in 1 (Z = C), thus promoting the formation of highly symmetrical metal/carbonate networks with cubic symmetry and sodalite-like topology. [1] The arrangement seen in 1 (Z = B) is present in some highly symmetrical cubic guanidinium borate derivatives we discovered recently which have the boracite topology. [2] A closely related hydrogen-bonding mode, again as in 1 (Z = S), is seen in a range of guanidinium sulfonates in which the sulfonate units, as well as the guanidinium components, act as 3-connecting nodes, each being attached to three guanidinium units as in 2.…”

Cubic, Hydrogen‐Bonded (10,3)‐a Networks in the Family [C(NH2)3][N(CH3)4][XO4] (X=S, Cr, and Mo)

“…Although numbers of metal/ligand‐bonded frameworks with the (10,3)‐ a topology are now increasing, hydrogen‐bonded examples such as the ones reported here remain rare 11. The results presented here, together with others,1, 2 indicate the potential of the guanidinium cation as a structure‐directing ion for the generation of new networks of high symmetry. These are possibilities we are actively pursuing.…”

“…The six hydrogen atoms of the cation are nicely disposed to form a pair of hydrogen bonds to each of three oxyanions, as shown in the generalized representation 1 In an extensive family of carbonate‐bridged coordination polymers reported recently, the guanidinum cation plays the crucial structural role represented in 1 (Z=C), thus promoting the formation of highly symmetrical metal/carbonate networks with cubic symmetry and sodalite‐like topology 1. The arrangement seen in 1 (Z=B) is present in some highly symmetrical cubic guanidinium borate derivatives we discovered recently which have the boracite topology 2.…”

Metal–Organic Replica of Fluorite Built with an Eight‐Connecting Tetranuclear Cadmium Cluster and a Tetrahedral Four‐Connecting Ligand

“…[5] CaB 6 , [6] feldspar, [7] NbO, [8] perovskite, [9] Pt 3 O 4 , [10] PtS, [7,11] pyrite, [12] quartz, [13] rutile, [14] sodalite, [15] SrSi 2 , [16] and tungsten bronze. [17] Note that the connectivity of the building blocks in any of these frameworks does not exceed six and, in general, coordination networks with a local connectivity higher than six is very rare.…”