Superclusters: A Host–Guest Complex with a Cyclic Array of Three Bridged MoFe<sub>3</sub>S<sub>4</sub> Clusters

Koutmos, Markos; Coucouvanis, D.

doi:10.1002/anie.200460154

Cited by 14 publications

(11 citation statements)

References 24 publications

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“…Two other Mo-Fe-S triclusters have been prepared. 36,37 These lack a μ 3 -S atom; instead components are linked in large rings through bridges between iron atoms in different clusters.…”

Section: Resultsmentioning

confidence: 99%

The [MoFe₃S₄]²⁺ Oxidation State: Synthesis, Substitution Reactions, and Structures of Phosphine-Ligated Cubane-Type Clusters with the S = 2 Ground State

Holm

2011

Inorg. Chem.

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The cluster [(Tp)MoFe3S4(PEt3)3]1+ containing the cubane-type [MoFe3(μ3-S)4]2+ reduced core undergoes facile ligand substitution reactions at the iron sites leading to an extensive set of mono- and disubstituted species [(Tp)MoFe3S4(PEt3)3-nLn]1-n with L = halide, N3-, PhS-, PhSe-, R3SiO-, and R3SiS- and n = 1 and 2. Structures of 10 members of the set are reported. For two representative clusters, Curie behavior at 2-20 K indicates a spin-quintet ground state. Zero-field Mössbauer spectra consist of two doublets in a 2:1 intensity ratio. 57Fe isomer shifts are consistent with the mean oxidation state Fe32.33+ arising from electron delocalization of the mixed-valence oxidation state description [Mo3+Fe3+Fe2+2]. Reaction of [(Tp)MoFe3S4(PEt3)2Cl] with (Me3Si)2S affords [(Tp)MoFe3S4(PEt3)2(SSiMe3)], a likely first intermediate in the formation of the tricluster compound {[(Tp)MoFe3S4(PEt)2]3S}(BPh4) from the reaction of [(Tp)MoFe3S4(PEt3)3](BPh4) and NaSSiMe3 in THF. The tricluster consists of three cluster units bound to a central μ3-S atom in a species of overall C3 symmetry. Relatively few clusters in the [MoFe3S4]2+ oxidation state have been prepared compared to the abundance of clusters in the oxidized [MoFe3S4]3+ state. This work is the first comprehensive study of the [MoFe3S4]2+ state, one conspicuous feature of which is its ability to bind hard and soft σ-donors and strong to weak π-acid ligands. (Tp = tris(pyrazolyl)hydroborate(1-))

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“…Two other Mo-Fe-S triclusters have been prepared. 36,37 These lack a μ 3 -S atom; instead components are linked in large rings through bridges between iron atoms in different clusters.…”

Section: Resultsmentioning

confidence: 99%

The [MoFe₃S₄]²⁺ Oxidation State: Synthesis, Substitution Reactions, and Structures of Phosphine-Ligated Cubane-Type Clusters with the S = 2 Ground State

Holm

2011

Inorg. Chem.

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“…Polymeric clusters, such as 1-D, 2-D, and 3-D clusters, have shown already good third-order optical nonlinearities or strong OL effects, but the origin of these good NLO properties is still not completely understood, and both ESA and TPA are claimed as responsible for the detected NLO performances. ,, On the basis of the previous research achievements on the third-order optical nonlinearity of these heterothiometallic clusters, the experimentally obtained nonlinearities for all types of clusters could be explained by the third-order susceptibility χ (3) , hence treating the system in a quasi-steady state. − ,,,,,,− …”

Section: Inorganic Materialsmentioning

confidence: 95%

“…Transition metal clusters possess interesting intrinsic electronic, optical, and structural properties. − Moreover, these can be used as precursor molecules of optical functional materials for optical signal detection techniques. − Currently, significant research interest in these clusters mainly stemmed from the search for new better materials with third-order NLO properties and superior OL effects …”

Section: Inorganic Materialsmentioning

confidence: 99%

Nonlinear Optical Materials for the Smart Filtering of Optical Radiation

2016

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The control of luminous radiation has extremely important implications for modern and future technologies as well as in medicine. In this Review, we detail chemical structures and their relevant photophysical features for various groups of materials, including organic dyes such as metalloporphyrins and metallophthalocyanines (and derivatives), other common organic materials, mixed metal complexes and clusters, fullerenes, dendrimeric nanocomposites, polymeric materials (organic and/or inorganic), inorganic semiconductors, and other nanoscopic materials, utilized or potentially useful for the realization of devices able to filter in a smart way an external radiation. The concept of smart is referred to the characteristic of those materials that are capable to filter the radiation in a dynamic way without the need of an ancillary system for the activation of the required transmission change. In particular, this Review gives emphasis to the nonlinear optical properties of photoactive materials for the function of optical power limiting. All known mechanisms of optical limiting have been analyzed and discussed for the different types of materials.

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“…But in the course of this research, a wealth of information on synthetic clusters resembling the FeMoco has been gained, and some of these clusters show some reactivity towards N 2 [122][123][124]. Another approach is to design an inorganic solid catalyst for low-temperature ammonia synthesis.…”

Section: Model Catalystsmentioning

confidence: 98%

Catalysis by Enzymes: The Biological Ammonia Synthesis

2006

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Enzymes are nature's own catalysts and fundamental for life, as they catalyze essentially all biological processes. Compared to inorganic catalysts, however, their structure and function is immensely more complicated. Computational . modeling has played an increasing role in elucidating enzyme mechanisms, as it can provide information complementary to experimental techniques. Elucidating enzyme structure and mechanism is not only important to understand the basic functions of life, they can also help to find and develop inorganic catalysts. In this review, an overview of recent computational developments for the enzyme nitrogenase will be given. Nitrogenase catalyzes ammonia synthesis, which is also a very important reaction in inorganic catalysis, and insight on enzyme structure and function could provide understanding on how to design biomimetic catalysts for low temperature ammonia synthesis.

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Superclusters: A Host–Guest Complex with a Cyclic Array of Three Bridged MoFe₃S₄ Clusters

Cited by 14 publications

References 24 publications

The [MoFe₃S₄]²⁺ Oxidation State: Synthesis, Substitution Reactions, and Structures of Phosphine-Ligated Cubane-Type Clusters with the S = 2 Ground State

The [MoFe₃S₄]²⁺ Oxidation State: Synthesis, Substitution Reactions, and Structures of Phosphine-Ligated Cubane-Type Clusters with the S = 2 Ground State

Nonlinear Optical Materials for the Smart Filtering of Optical Radiation

Catalysis by Enzymes: The Biological Ammonia Synthesis

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Superclusters: A Host–Guest Complex with a Cyclic Array of Three Bridged MoFe3S4 Clusters

Cited by 14 publications

References 24 publications

The [MoFe3S4]2+ Oxidation State: Synthesis, Substitution Reactions, and Structures of Phosphine-Ligated Cubane-Type Clusters with the S = 2 Ground State

The [MoFe3S4]2+ Oxidation State: Synthesis, Substitution Reactions, and Structures of Phosphine-Ligated Cubane-Type Clusters with the S = 2 Ground State

Nonlinear Optical Materials for the Smart Filtering of Optical Radiation

Catalysis by Enzymes: The Biological Ammonia Synthesis

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Product

Resources

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Superclusters: A Host–Guest Complex with a Cyclic Array of Three Bridged MoFe₃S₄ Clusters

The [MoFe₃S₄]²⁺ Oxidation State: Synthesis, Substitution Reactions, and Structures of Phosphine-Ligated Cubane-Type Clusters with the S = 2 Ground State

The [MoFe₃S₄]²⁺ Oxidation State: Synthesis, Substitution Reactions, and Structures of Phosphine-Ligated Cubane-Type Clusters with the S = 2 Ground State