Spontaneously Organizing Metal Connectors as Supramolecular Structure Directors of Two‐ and Three‐Dimensional Organometallic Assemblies

Abstract

The supramolecular interplay of Me(3)Sn(+) and [M(CN)(2n)](n-) ions (n=3 and 4) with either 4,4'-bipyridine (bpy), trans-bis(4-pyridyl)ethene (bpe) or 4cyanopyridine (cpy) in the presence of H(2)O has been investigated for the first time. Crystal structures of the six novel assemblies: [(Me(3)Sn)(4)Mo(IV)(CN)(8).2 H(2)O.bpy] (8) and [(Me(3)Sn)(4)Mo(IV)(CN)(8).2 H(2)O.bpe] (8 a; isostructural), [(Me(3)Sn)(3)Fe(III)(CN)(6).4 H(2)O.bpy] (9), [(Me(3)Sn)(3)Co(III)(CN)(6).3 H(2)O.3/2 bpy] (10), [(Me(3)Sn)(4)Fe(II)(CN)(6).H(2)O.3/2 bpy] (11), and [(Me(3)Sn)(4)Ru(II)(CN)(6).2 H(2)O.3/2 cpy] (12) are presented. H(2)O molecules are usually coordinated to tin atoms and involved in two significant O-H.N hydrogen bonds, wherein the nitrogen atoms belong either to bpy (bpe, cpy) molecules or to M-coordinated cyanide ligands. Extended supramolecular assemblies such as -CN-->Sn(Me(3))<--O(H.)H.N(L)N.HO(H.)-->Sn(Me(3))<--NC- (L=bpy, bpe or cpy) function as efficient metal connectors (or spacers) in the structures of all six compounds. Only in the three-dimensional framework of 11, one third of all bpy molecules is involved in coordinative N-->Sn bonds. The supramolecular architecture of 9 involves virtually non-anchored (to cyanide N atoms), Me(3)Sn(+) units with a strictly planar SnC(3) skeleton, and two zeolitic H(2)O molecules. Pyrazine (pyz) is surprisingly reluctant to afford assemblies similar to 8-12, however, the genuine host-guest systems [(Me(3)Sn)(4)Mo(CN)(8).0.5pyz] and [(Me(3)Sn)(4)Mo(CN)(8).pym] (pym=pyrimidine) could be isolated and also structurally characterized.

A New Family of Bimetallic Framework Materials Showing Reversible Structural Transformations

“…52 The metal coordination environment of the hexacyanocobaltate(III) moiety is in good agreement with reported structures. 53,54 The Cd-N bond lengths vary from 2.318(2) to 2.416(2) Å. Five of the six CN groups are bridging, while the sixth hydrogen bonds to water O3w located in the channel (Figure 2a).…”

New supramolecular organotin(IV)/-copper(I) cyanides containing the unique {CuI2(μ-CN)2} building block

“…IR spectrum (cm (1 ): 2095s (nCN), 452s (nCuC); vibrational modes of pdvb: 3047m, 2988m, 1598s, 1531s, 1480s, 1427s, 728s, 694s. All crystallization experiments according to route 2 (vide supra) were conducted as described earlier [14,15].…”

“…The second route makes use of the very slow transfer of Me 3 SnCl molecules from the gas phase above a sample of solid Me 3 SnCl (or of a concentrated aqueous solution) into an aqueous solution of K 3 [Cu(CN) 4 ], the bipodal base L and a small quantity of MeCN [14,15]. A third, rather promising route, which has, however, not yet been applied for the preparation of organotincontaining species, is the so-called 'thiosulfate-assisted' method which is carried out in aqueous solution [9].…”

Characterization of a chiral menthyldimethyltin molybdate and its use as an olefin epoxidation catalyst

“…One of the most appealing strategies is the formation of coordination networks through the aggregation via intermolecular bonds of two or more modular units. The self-assembly of organotin cationic fragments such as Me 3 Sn + with different anionic metal-containing species has provided a large family of supramolecular organometallic networks with either 1-dimensional (1D), 2D or 3D architectures [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23]. In 1993 Fischer and co-workers described a series of compounds with the general formula [(R 3 E) 2 MO 4 ] (R = Me, Et, nPr, nBu, or Ph; E = Sn or Pb; M = Mo or W) [19].…”