Cubic and rhombohedral heterobimetallic networks constructed from uranium, transition metals, and phosphonoacetate: new methods for constructing porous materials

Alsobrook, Andrea N.; Hauser, Bernard A.; Hupp, Joseph T.; Alekseev, Evgeny V.; Depmeier, Wulf; Albrecht‐Schmitt, Thomas E.

doi:10.1039/c0cc03507f

Cited by 111 publications

(66 citation statements)

References 28 publications

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“…The mean MnO yl (where O yl is the uranyl oxygen atom) bond length in 1 is 2.055(6) Å, significantly shorter than that found in the heteronuclear {U 12 Mn 6 } wheel (2.15(2) Å)8f and in a heterodimetallic uranyl(VI)–manganese(II) complex (2.163(4) Å) 12. In compound 2 , the CdO yl distance (2.201(16) Å) is slightly shorter than that found in a Cd–uranyl(V) polymer complex (2.28(2) Å),13 and in a heterodimetallic U VI /Cd II system (2.252(4) Å) 13. The mean U‐O‐M angle measures 169.7(1.7)° in 1 and 168.7(8)° in 2 , whereas the M‐U‐M angle is 173.77(5)° in 1 and 174.86(6)° in 2 .…”

Section: Methodsmentioning

confidence: 87%

Self‐Assembly of a 3d–5f Trinuclear Single‐Molecule Magnet from a Pentavalent Uranyl Complex

et al. 2014

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Mixed-metal uranium compounds are very attractive candidates in the design of single-molecule magnets (SMMs), but only one 3d-5f hetero-polymetallic SMM containing a uranium center is known. Herein, we report two trimeric heterodimetallic 3d-5f complexes self-assembled by cationcation interactions between a uranyl(V) complex and a TPA-capped M II complex (M = Mn (1), Cd (2); TPA = tris(2-pyridylmethyl)amine). The metal centers were strategically chosen to promote the formation of discrete molecules rather than extended chains. Compound 1, which contains an almost linear {Mn À O = U = O À Mn} core, exhibits SMM behavior with a relaxation barrier of 81 AE 0.5 K-the highest reported for a mono-uranium system-arising from intramolecular Mn-U exchange interactions combined with the high Ising anisotropy of the uranyl(V) moiety. Compound 1 also exhibits an open magnetic hysteresis loop at temperatures less than 3 K, with a significant coercive field of 1.9 T at 1.8 K.Uranium compounds have been identified as attractive candidates in the search for new molecules displaying slow magnetic relaxation of a purely molecular origin (i.e. singlemolecule magnets, or SMMs). [1] The high magnetic anisotropy of the uranium ion over a range of oxidation states, combined

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Section: Methodsmentioning

confidence: 87%

Self‐Assembly of a 3d–5f Trinuclear Single‐Molecule Magnet from a Pentavalent Uranyl Complex

et al. 2014

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“…These chains are connected by Mn-centered moieties through Mn O P and Mn O U interactions, leading to the 3D heterometallic uranyl phosphonoacetate (Fig. 32b) [ [70][71][72] owing to the high-symmetry and porosity. The structure crystallizes in the highly symmetrical cubic space group Im-3, which is exceedingly rare for uranyl compounds.…”

Section: Heterometallic Uranyl Compounds With Carboxyphosphonate Ligandsmentioning

confidence: 99%

“…The cadmium uranyl phosphonoacetate Cd 3 (UO 2 ) 6 (H 2 O) 13 (PPA) 6 ·6H 2 O [71,72] is also remarkable in that it crystallizes in the rhombohedral space group R-3 and features a nano-sized channel along the c-axis, which is uncommon in uranyl phosphonate compounds (Fig. 34).…”

Section: Heterometallic Uranyl Compounds With Carboxyphosphonate Ligandsmentioning

confidence: 99%

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Structural chemistry of uranium phosphonates

Yang

Parker

Sun

2015

Coordination Chemistry Reviews

127

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“…as gas sensor, catalyst,, and ion exchanger . Zinc 5‐phosphonobenzene‐1,3‐dicarboxylate acts as catalyst in Friedel‐Crafts benzylation reactions and a selective CO 2 uptake was observed for cobalt uranyl phosphonoacetate and indium 4′‐phosphonobiphenyl‐3,5‐dicarboxlyate . Ion exchange properties were found for example titanium‐, chromium‐, and aluminum 3‐phosphono‐hydrogenpropionate and zirconium diphosphonate‐phosphate hybrids, whereas cobalt 1‐(methylenephosphono)‐pyrrolidine‐2‐carboxylate can be used as catalyst for water oxidation .…”

Section: Introductionmentioning

confidence: 99%

Crystal Structure and Characterization of Two Layered Copper(II) Coordination Polymers with Anions of 3‐Phosphonopropionic Acid and (RS)‐2‐Phosphonobutyric Acid

Köferstein

Arnold

Robl

2018

Zeitschrift anorg allge chemie

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Blue single crystals of Cu[μ 3 -O 3 P(CH 2 ) 2 COOH]·2H 2 O (1) and Cu[(RS)-μ 3 -O 3 PCH(C 2 H 5 )COOH]·3H 2 O (2) were prepared in aqueous solutions (pH = 2.5-3.5). 1 crystallizes in space group Pbca (no. 61) with a = 812.5(2), b = 919.00(9), and c = 2102.3(2) pm. Cu 2+ is fivefold coordinated by three oxygen atoms stemming from [O 3 P(CH 2 ) 2 COOH] 2anions and two water molecules. The Cu-O bond lengths range from 194.0(3) to 231.8(4) pm. The connection between the [O 3 P(CH 2 ) 2 COOH] 2anions and the Cu 2+ cations yields a polymeric structure with layers parallel to (001). The layers are linked by hydrogen bonds. 2 crystallizes in space group Pbca (no. 61) with a = 1007.17 (14), b = 961.2(3), c = 2180.9(4) pm. The copper cations are surrounded by five oxygen atoms in a square pyramidal fashion 205 with Cu-O bonds between 193.6(4) and 236.9(4) pm. The coordination between [O 3 PCH(C 2 H 5 )COOH] 2and Cu 2+ results in infinite puckered layers parallel to (001). The layers are not connected by any hydrogen bonds. Each layer contains both R and S isomers of the [O 3 PCH(C 2 H 5 )COOH] 2dianion. Water molecules not bound to Cu 2+ are intercalated between the layers. UV/Vis spectra suggest three d-d transition bands at 743, 892, 1016 nm for 1 and four bands at 741, 838, 957, and 1151 nm for 2, respectively. Magnetic measurements suggest a weak antiferromagnetic coupling between Cu 2+ due to a super-superexchange interaction. Thermoanalytical investigations in air show that the compounds are stable up to 95°C (1) and 65°C (2), respectively.

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Cubic and rhombohedral heterobimetallic networks constructed from uranium, transition metals, and phosphonoacetate: new methods for constructing porous materials

Cited by 111 publications

References 28 publications

Self‐Assembly of a 3d–5f Trinuclear Single‐Molecule Magnet from a Pentavalent Uranyl Complex

Self‐Assembly of a 3d–5f Trinuclear Single‐Molecule Magnet from a Pentavalent Uranyl Complex

Structural chemistry of uranium phosphonates

Crystal Structure and Characterization of Two Layered Copper(II) Coordination Polymers with Anions of 3‐Phosphonopropionic Acid and (RS)‐2‐Phosphonobutyric Acid

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