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Title: Self-Assembly of Hexanuclear Clusters of 4f and 5f Elements with Cation Specificity

Abstract

Six hexanuclear clusters of 4f and 5f elements were synthesized by room-temperature slow concentration experiments. Cerium(IV), thorium(IV), and plutonium(IV) each form two different hexanuclear clusters, among which the cerium and plutonium clusters are isotypic, whereas the thorium clusters show more diversity. The change in ionic radii of approximately 0.08 Å between these different metal ions tunes the cavity size so that NH{sub 4}{sup +} (1.48 Å) has the right dimensions to assemble the cerium and plutonium clusters, whereas Cs{sup +} (1.69 Å) is necessary to assemble the thorium clusters. If these cations are not used in the reactions, only amorphous material is obtained.

Authors:
; ; ;
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC); Materials Science of Actinides (MSA)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1064913
DOE Contract Number:
SC0001089
Resource Type:
Journal Article
Resource Relation:
Journal Name: European Journal of Inorganic Chemistry; Journal Volume: 9; Journal Issue: 9; Related Information: MSA partners with University of Notre Dame (lead); University of California, Davis; Florida State University; George Washington University; University of Michigan; University of Minnesota; Oak Ridge National Laboratory; Oregon state University; Rensselaer Polytechnic Institute; Savannah River National Laboratory
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; nuclear (including radiation effects), materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly)

Citation Formats

Diwu, J., Good, Justin J., DiStefano, Victoria H., and Albrecht-Schmitt, Thomas E. Self-Assembly of Hexanuclear Clusters of 4f and 5f Elements with Cation Specificity. United States: N. p., 2011. Web. doi:10.1002/ejic.201100066.
Diwu, J., Good, Justin J., DiStefano, Victoria H., & Albrecht-Schmitt, Thomas E. Self-Assembly of Hexanuclear Clusters of 4f and 5f Elements with Cation Specificity. United States. doi:10.1002/ejic.201100066.
Diwu, J., Good, Justin J., DiStefano, Victoria H., and Albrecht-Schmitt, Thomas E. 2011. "Self-Assembly of Hexanuclear Clusters of 4f and 5f Elements with Cation Specificity". United States. doi:10.1002/ejic.201100066.
@article{osti_1064913,
title = {Self-Assembly of Hexanuclear Clusters of 4f and 5f Elements with Cation Specificity},
author = {Diwu, J. and Good, Justin J. and DiStefano, Victoria H. and Albrecht-Schmitt, Thomas E.},
abstractNote = {Six hexanuclear clusters of 4f and 5f elements were synthesized by room-temperature slow concentration experiments. Cerium(IV), thorium(IV), and plutonium(IV) each form two different hexanuclear clusters, among which the cerium and plutonium clusters are isotypic, whereas the thorium clusters show more diversity. The change in ionic radii of approximately 0.08 Å between these different metal ions tunes the cavity size so that NH{sub 4}{sup +} (1.48 Å) has the right dimensions to assemble the cerium and plutonium clusters, whereas Cs{sup +} (1.69 Å) is necessary to assemble the thorium clusters. If these cations are not used in the reactions, only amorphous material is obtained.},
doi = {10.1002/ejic.201100066},
journal = {European Journal of Inorganic Chemistry},
number = 9,
volume = 9,
place = {United States},
year = 2011,
month = 2
}
  • Six hexanuclear clusters of 4f and 5f elements were synthesized by room-temperature slow concentration experiments. Cerium(IV), thorium(IV), and plutonium(IV) each form two different hexanuclear clusters, among which the cerium and plutonium clusters are isotypic, whereas the thorium clusters show more diversity. The change in ionic radii of approximately 0.08 Å between these different metal ions tunes the cavity size so that NH4+ (1.48 Å) has the right dimensions to assemble the cerium and plutonium clusters, whereas Cs+ (1.69 Å) is necessary to assemble the thorium clusters. If these cations are not used in the reactions, only amorphous material is obtained.
  • The coordination of [Mo{sub 6}Cl{sub 8}{sup i}(SO{sub 3}CF{sub 3}){sub 6}{sup a}]{sup 2-} (1) and [Mo{sub 6}Cl{sub 8}{sup I}Cl{sub 4}{sup a}(EtOH){sup a}{sub 2}] (2) to poly(e-vinylpyridine) (PVP) produces crosslinked materials. Formation of these materials occurs by displacement of axial ligands SO{sub 3}CF{sub 3}{sup -} or EtOH on the clusters by the vinylpyridine moieties. The availability of six coordination sites in 1 and two coordination sites in 2 offers control over the degree of crosslinking and solubility of the materials. Similarly, varying the ratio of cluster coordination sites (C) to polymer-pendent pyridine ligands (P) yields materials with a wide range of solubilitiesmore » and glass transition temperatures (T{sub g}). Materials with C:P ratios of 1:100 are highly soluble in CH{sub 2}Cl{sub 2} and MeOH, with T{sub g} are obtained with C:P ratios of 1:5 and lower, indicating a high degree of crosslinks. Transient emission spectroscopy reveals that polymer-bound cluster 1 lacks the luminescent properties characteristic of many [Mo{sub 6}Cl{sub 8}]{sup 4+} based clusters. Conversely, polymer-bound cluster 2 displays intense luminescence and retains the unusually long-lived excited-state observed for the free clusters in solution. The emission lifetime of PVP-bound 2 fits a biexponential decay, with {tau}{sub 1} = 90 {mu}s (60%) and {tau}{sub 2} = 8 {mu}s (40%), while [Mo{sub 6}Cl{sub 8}{sup i}Cl{sub 6}{sup a}]{sup 2-} has a uniexponential decay of {tau} = 156 {mu}s in CH{sub 2}Cl{sub 2} solution.« less
  • The authors wished to examine the W{sub 6}Te{sub 8} complexes with the idea that the W{sub 6}Te{sub 8} binary compound might be more stable toward disproportionation than the W{sub 6}S{sub 8}{sup 6a} and W{sub 6}Se{sub 8} examples. In this paper, the authors report the synthesis and structures of the first two molecular telluride complexes with M{sub 6}Te{sub 8}{sup {minus}} and M{sub 6}Te{sub 8} (M = Mo, W) cluster cores.
  • Relatively little attention has been paid to metal ions with the nd[sup 10] and nd[sup 10](n+1)s[sup 2] (i.e., [open quotes]s[sup 2][close quotes]) configurations. In combination with various anionic and neutral ligands, these metal ions form a wide variety of cluster compounds, some of which have been known to be luminescent when irradiated with ultraviolet light. Prominent examples of this family are cuprous iodide clusters such as Cu[sub 4]I[sub 4]-(py)[sub 4] (1, py = pyridine), which shows [open quotes]luminescence thermochromism[close quotes]; that is, they display bright emissions with colors markedly dependent on the temperature. Here the authors present an overview ofmore » recent studies carried out both independently and jointly in the authors' laboratories focusing upon the remarkably rich, but relatively unexplored, photochemical and photophysical properties of various tetra-and hexanuclear d[sup 10] and s[sup 2] metal ion clusters in solution. 74 refs., 4 figs., 2 tabs.« less
  • The carbene-containing cluster complex Os/sub 3/(CO)/sub 9/(C(H)NMe/sub 2/)..mu..-SMe)(..mu..-H) (1) was prepared in 56% yield from the reaction of Os/sub 3/(CO)/sub 10/(..mu..-SMe)(..mu..-H) with CH/sub 2/(NMe/sub 2/)/sub 2/. UV irradiation of 1 yielded the complex Os/sub 3/(CO)/sub 8/(..mu..-CNMe/sub 2/)(..mu..-SMe)(..mu..-H)/sub 2/ (2) in 68% yield. Compound 2 contains a bridging (dimethylamino)carbyne ligand that was formed by an ..cap alpha..-CH activation of the carbene ligand in 1. Thermal decarbonylation of 2 resulted in the formation of the hexaosmium cluster complex Os/sub 6/-(CO)/sub 12/(..mu..-CNMe/sub 2/)/sub 2/(..mu..-SMe)/sub 2/(..mu..-H)/sub 2/ (3) in 65% yield. Compound 3 was characterized by a single-crystal X-ray diffraction analysis. The structure wasmore » solved by a combination of direct methods and difference Fourier techniques and was refined (2701 reflections) to the final values of the residuals R = 0.048 and R/sub w/ = 0.050. The structure consists of six osmium atoms arranged in the form of two tetrahedral clusters that have one edge in common. There are two bridging (dimethylamino)carbyne ligands and two triply bridging methanethiolato ligands that appear to serve as three-electron donors instead of the usual five-electron-donor configuration. 18 references, 3 figures, 4 tables.« less