Family of Polynuclear Nickel Cagelike Phenylsilsesquioxanes; Features of Periodic Networks and Magnetic Properties

Abstract

A new family of bi-, tetra-, penta-, and hexanickel cagelike phenylsilsesquioxanes 1-6 was obtained by self-assembly and transmetalation procedures. Their crystal structures were established by single-crystal X-ray analysis, and features of crystal packing relevant to the network formation were studied by a topological analysis. Compounds 1, 2, and 4 are isolated architectures, while 3, 5, and 6 present extended 1D and 3D networks. The investigation of magnetic properties revealed the presence of ferro- (1 and 3-5) or antiferromagnetic (2 and 6) interactions between Ni(II) ions, giving rise in the most cases (1, 2, and 4-6) to the presence of a slow relaxation of the magnetization, which can originate from the spin frustration.

Heptanuclear Cage CuII‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity

“…The general feature is a prismatic (drumlike) molecular geometry with two tetradeca‐membered siloxane cycles coordinating the central copper oxide layer. The only observation of tetradeca‐membered siloxane ligands involved in the formation of metallasilsesquioxane cages has been recently reported by some of us for a Ni 2 ‐based compound . In turn, to the best of our knowledge, compounds 1 and 2 are the first representatives of heptanuclear cage silsesquioxanes.…”

A Carbonate-Templated Decanuclear Mn Nanocage with Two Different Silsesquioxane Ligands

“…Generally, the silsesquioxane ligands are available via in situ hydrolysis and condensation of the key precursor {RSi­(OR′) 3 }. So far, there have been cyclic, acyclic, and polycyclic types of the oligomeric silsesquioxanes with different condensation degrees (i.e., different number of [Si] atoms) being established (e.g., [Si1], , [Si4], − [Si5], , [Si6], ,,− [Si7], − [Si8], [Si9], [Si10], ,, and [Si12]). These various incompletely condensed silsesquioxanes may provide more possibilities to modulate the aggregation of metal ions.…”

Palanquin-Like Cu4Na4 Silsesquioxane Synthesis (via Oxidation of 1,1-bis(Diphenylphosphino)methane), Structure and Catalytic Activity in Alkane or Alcohol Oxidation with Peroxides

“…Cage metallasilsesquioxanes (CLMSs) [1][2][3][4][5][6][7][8][9][10] are popular objects for the investigation of regularities in the insertion of metal ions into the siloxane matrix [11][12][13][14][15][16][17][18], the study of catalytic [19][20][21][22][23][24] properties, magnetic (spin) glass [25], as well as the study of nanoparticles [26] and macrocyclic siloxane material [27] formation.…”