Novel Concentration-Driven Structural Interconversion in Shape-Specific Solids Supported by the Octahedral [Re₆(μ₃-Se)₈]²⁺ Cluster Core

Abstract

A complex containing the face-capped octahedral [Re(6)(mu(3)-Se)(8)](2+) cluster core, cis-[Re(6)(mu(3)-Se)(8)(PPh(3))(4)(4,4'-dipyridyl)(2)](SbF(6))(2) (1), is used as a ditopic ligand with an enforced right angle between the two 4,4'-dipyridyl moieties for the coordination of Cd(2+) ion. Two coordination polymers, [[Re(6)(mu(3)-Se)(8)(PPh(3))(4)(4,4'-dipyridyl)(2)](2)[Cd(NO(3))(2)]](SbF(6))(4).21C(4)H(10)O.21CH(2)Cl(2) (2) and [[Re(6)(mu(3)-Se)(8)(PPh(3))(4)(4,4'-dipyridyl)(2)][Cd(NO(3))(3)]](NO(3)).2C(4)H(10)O.CH(2)Cl(2) (3), are obtained. The relative concentration of Cd(2+) determines which species is isolated, and the conversion of the first structure into the second is demonstrated experimentally.

Self‐Assembly of Cluster‐Based Nanoscopic Supramolecules into One‐Dimensional Coordination Polymers

“…Hydrogen bonds between nonbridging cyanides and the aqua ligands further connect the chains into layers (Figure 2(a)) which are held together through hydrogen bonding between disordered water molecules. The connectivity mode {Nb 6 }-C≡N-Mn-L bridge -Mn-N≡C-{Nb 6 } observed in the three compounds is different from that observed in a series of {Re 6 } based compounds in which ({Re 6 }-L bridge -M-L bridge -{Re 6 }) is observed [84][85][86][87]. Simultaneous use of CN and ditopic ligands as bridges has been observed in mononuclear cyanometallate-based coordination polymers [88][89][90][91][92][93], however similar structures have never been reported for cluster-based coordination networks.…”

Octahedral chalcogenide rhenium cluster complexes with imidazole

“…Alternatively, furnishing the clusters with polymerisable ligands gives an opportunity to use the octahedral rhenium clusters as the active components of processable luminescent polymers [7,[29][30]. Synthesis of the metal clusters with simple heterocyclic ligands [9,[31][32][33][34] are also of interest, as such compounds that can lead to additional properties, which include supramolecular, porous crystalline structures [35][36][37] or versatile redox properties [27]. Moreover, the study of octahedral complexes with simple heterocycles that are related to biological molecules such as nucleotides and amino-acids may uncover the potential of these compound as, for example, anticancer agents [38].…”

Advances in the Engineering of Near Infrared Emitting Liquid Crystals and Copolymers, Extended Porous Frameworks, Theranostic Tools and Molecular Junctions Using Tailored Re6 Cluster Building Blocks

“…This chemistry has yielded a wide library of compounds with fascinating crystal structures and properties as superconductivity [9], thermoelectricity [10], intercalation/de-intercalation [11], Mott insulating behaviors [12] with potential applications, for instance, for energy conversion or the design of Random Access Memories (RAM). Besides their physical properties in the solid state, that originate from number of valence electrons per cluster available for metal-metal bonding and to the strength of electronic interactions between cluster units, many solid state compounds and in particular octahedral cluster compounds can be used as precursors to afford discrete soluble molecular species for the structuration and the design of molecular assemblies [13], extended molecular solids [14][15][16][17][18][19][20][21][22][23][24][25], supported materials and nanomaterials [21,26,27] that are of interest in the fields of hydrogen storage, sensors, imaging and displays.…”