In situ generated polysiloxanes stabilizing μ<sub>3</sub>-oxo bridged Sb<sub>3</sub> triangles

Prabhu, M.; Ugandhar, Uppara; Baskar, Viswanathan

doi:10.1039/c5dt01590a

Cited by 15 publications

(1 citation statement)

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“…Among those, particular interest has been devoted to the synthesis and investigations of cagelike polycyclic compounds based on silsesquioxane RSiO 1.5 building blocks, including different types of metal-containing derivatives . Different approaches have been employed to design such isolated architectures of various nuclearities, containing transition-metal ions or lanthanides linked through silicon atoms, including self-assembling reactions of tri- ,, or tetrasilanols as well as noncondensed cubane silsesquioxane ,, building blocks. Indeed, polynuclear architectures with various structural organizations, such as Ti-based adamantine, Cu-based Cooling Tower and Knight Helmet, Fe-based drum or In-based bird cage, Sn-based tricubanes, and Nd-based tetracubanes are available using these synthetic strategies.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2017

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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.

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Section: Introductionmentioning

confidence: 99%

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

et al. 2017

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Cage‐like Fe,Na‐Germsesquioxanes: Structure, Magnetism, and Catalytic Activity

et al. 2016

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As eries of four unprecedented heterometallic metallagermsesquioxanes were synthesized. Their cage-like architectures have au nique type of molecular topology consisting of the hexairon oxo{ Fe 6 O 19 }c ore surrounded in at riangular manner by three cyclic germoxanolates [PhGe-(O)O] 5 .T his structural organization induces antiferromagnetic interactions between the Fe III ions through the oxygen atoms.E valuated for this first time in catalysis,t hese compounds showed ah igh catalytic activity in the oxidation of alkanes and the oxidative formation of benzamides from alcohols.The design of metal-based polycyclicc age-like compounds has attracted ag reat deal of attention from researchers worldwide over several decades owing to their structural diversity and their potential technological applications especially in catalysis. [1] Numerous metal-oxygen clusters, [1b,c,j] metal-organic frameworks [1d,l,m] or metal-organic polyhedrons [1f,n] have been designed by using av ariety of selfassembling or templated reactions.A mong those,awide family of polynuclear cage-like metallasilsesquioxanes (CLMSs) architectures with interesting structural topologies [2] and important catalytic activity (e.g.i ne poxidation, oxidation and polymerization) [3] has been synthesized through ar eaction involving transition-metal ions and silsesquioxane [RSiO 1.5 ] n ligands.S urprisingly,e xamples of cage-like architectures involving another metalloid close to silicon, namely germanium, are scarce despite the great potential of this element in organometallic chemistry.T oour knowledge there is only aseries of compounds obtained from germasesquioxane [RGeO 1.5 ] 2 (R = HOOCCH 2 CH 2 )and various cations. [4] Their hydrothermal synthesis requires relatively hard conditions consisting of several days of reactions at 110 8 8C. It is worth mentioning that to date focus has only been on the synthesis,t hermogravimetric analysis,l uminescence, and sorption properties of these architectures and no investigation of the catalytic activity of metallagermanates has been reported.Herein, we report an alternative and simplified synthetic approach to design aseries of unprecedented individual cagelike metallagermsesquioxanes under mild conditions.I n addition, the catalytic activity and magnetic properties of the metallagermsesquioxanes will be discussed.Thes ingle crystals of Fe,Na-phenylgermsesquioxane [(Ph 5 Ge 5 O 10 ) 3 Fe 6 (OH) 3 (O)Na 2 ]·(EtOH) 2 ·H 2 O 1 (10 %y ield) were obtained by ar eaction between phenyltrimethoxygermane PhGe(OMe) 3 ,N aOH and anhydrous FeCl 3 in ethanol with further crystallization. Thea ddition of N-containing ligands,s uch as phenanthroline,b ipyridine,o rn eocuproine to this reaction allowed us to isolate complexes

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