Octahedral Metal Clusters [Nb₆Cl₁₂(CN)₆]^4– as Molecular Building Blocks: From Supramolecular Assemblies to Coordination Polymers

Abstract

There are considerable advantages for using metal clusters as building units of supramolecular materials because of their unique structural, chemical, and physical properties, all of which fall in between normal valence compounds and the metals. In this microreview, we describe the synthetic methodology and structural properties of recent findings in the use of octahedral niobium hexacyanochloride anions as building units of assemblies of different size, charge, and dimensionality. We focus on the use of a metal-directed approach to prepare cluster-based supramolecular assemblies

Supramolecular Frameworks Built up from Red‐Phosphor­escent trans‐Re6 Cluster Building Blocks: One Pot Synthesis, Crystal Structures, and DFT Investigations

“…Many 3D frameworks with topology related to Prussian blue or Super-Prussian blue series as well as layered structures have been reported in the literature. [26][27][28][29][30][31][32][33][34][35][36][37][48][49][50][51][52] Some of them could be relevant materials for the elaboration of chemical sensors. [28] A second strategy is the use of bidentate linkers.…”

Structural regularity and diversity in hybrids of aromatic thioethers and BiBr3: from discrete complexes to layers and 3D nets

“…1 H NMR (300 MHz, CDCl 3 ): d 2.48 (s, 12H), 7.14 (s, 16H), 7.45 (s, 2H). 13 (7). In a nitrogen-filled glovebox, L7 (5.0 mg, 8.8 mmol) and BiBr 3 (30.0 mg, 66.9 mmol) were loaded into a heavy-wall borosilicate glass tube, and benzene (0.4 mL, anhydrous) was added.…”

“…The offshoot BiBr 3 unit and the benzene guest are only partially occupied, and their occupancies are refined to 0.440(1) and 0.291 (7), respectively. Elemental analysis (found: C 23.87%, H 1.74%; calculated: C 24.16%, H 1.52%) is consistent with this occupancy factor assignment.…”

The Crystallization of Extended Niobium-Cluster Framework Compounds: A Novel Approach Using Ionic Liquids

“…In the field of Nb 6 -based cluster compounds, Lachgar and co-workers published Prussian-blue analogue cluster networks, by connecting cyanide ligated [Nb 6 Cl 12 ] units via manganese­(II) cations . In the following years, more work was published exploring the bridging of dissolved cluster units through CN groups. − To the best of our knowledge, so far, no further functionalization at the exo ligand sites of M 6 cluster units, besides cyanide groups, aiming for framework compounds was performed. In this paper, we report about an expansion of this cluster-reconnecting principle, using isothiocyanato functionalized Nb 6 cluster cores.…”