Anti-Bimetallic Complexes of Divalent Lanthanides with Silylated Pentalene and Cyclooctatetraenyl Bridging Ligands as Molecular Models for Lanthanide-Based Polymers

2009 ◽  
Vol 28 (20) ◽  
pp. 5896-5908 ◽  
Author(s):  
Owen T. Summerscales ◽  
Simon C. Jones ◽  
F. Geoffrey N. Cloke ◽  
Peter B. Hitchcock
Keyword(s):  
Bimetallic Complexes ◽  
Molecular Models ◽  
Bridging Ligands

Luminescent EuIII and TbIII bimetallic complexes of N,N′-heterocyclic bases and tolfenamic acid: structures, photophysical aspects and biological activity

2020 ◽  
Vol 44 (36) ◽  
pp. 15685-15697
Author(s):  
Zafar Abbas ◽  
Prerana Singh ◽  
Srikanth Dasari ◽  
Sri Sivakumar ◽  
Ashis K. Patra
Keyword(s):  
Biological Activity ◽  
Cellular Imaging ◽  
Tolfenamic Acid ◽  
Bimetallic Complexes ◽  
Bridging Ligands ◽  
Imaging Capability ◽  
Heterocyclic Bases

The isostructural bimetallic luminescent EuIII and TbIII dimers containing N,N′-heterocyclic bases and tolfenamic acid as a bridging ligands were evaluated for their structures, cellular imaging capability and photocytotoxicity.

Tuning the Redox Activity of Metal−Organic Frameworks for Enhanced, Selective O2 Binding

2019 ◽  
Author(s):  
Andrew Rosen ◽  
M. Rasel Mian ◽  
Timur Islamoglu ◽  
Haoyuan Chen ◽  
Omar Farha ◽  
...  
Keyword(s):  
Density Functional ◽  
Metal Organic Frameworks ◽  
Redox Activity ◽  
Screening Methods ◽  
Bridging Ligands ◽  
Metal Centers ◽  
Computational Screening ◽  
Open Metal Sites ◽  
Metal Organic ◽  
Unsaturated Metal Sites

<p>Metal−organic frameworks (MOFs) with coordinatively unsaturated metal sites are appealing as adsorbent materials due to their tunable functionality and ability to selectively bind small molecules. Through the use of computational screening methods based on periodic density functional theory, we investigate O<sub>2</sub> and N<sub>2</sub> adsorption at the coordinatively unsaturated metal sites of several MOF families. A variety of design handles are identified that can be used to modify the redox activity of the metal centers, including changing the functionalization of the linkers (replacing oxido donors with sulfido donors), anion exchange of bridging ligands (considering μ-Br<sup>-</sup>, μ-Cl<sup>-</sup>, μ-F<sup>-</sup>, μ-SH<sup>-</sup>, or μ-OH<sup>-</sup> groups), and altering the formal oxidation state of the metal. As a result, we show that it is possible to tune the O<sub>2</sub> affinity at the open metal sites of MOFs for applications involving the strong and/or selective binding of O<sub>2</sub>. In contrast with O<sub>2</sub> adsorption, N<sub>2</sub> adsorption at open metal sites is predicted to be relatively weak across the MOF dataset, with the exception of MOFs containing synthetically elusive V<sup>2+</sup> open metal sites. As one example from the screening study, we predict that exchanging the μ-Cl<sup>-</sup> ligands of M<sub>2</sub>Cl<sub>2</sub>(BBTA) (H<sub>2</sub>BBTA = 1<i>H</i>,5<i>H</i>-benzo(1,2-d:4,5-d′)bistriazole) with μ-OH<sup>-</sup> groups would significantly enhance the strength of O<sub>2</sub> adsorption at the open metal sites without a corresponding increase in the N<sub>2</sub> affinity. Experimental investigation of Co<sub>2</sub>Cl<sub>2</sub>(BBTA) and Co<sub>2</sub>(OH)<sub>2</sub>(BBTA) confirms that the former exhibits only weak physisorption, whereas the latter is capable of chemisorbing O<sub>2</sub> at room temperature. The chemisorption behavior is attributed to the greater electron-donating character of the μ-OH<sup>-</sup><sub> </sub>ligands and the presence of H-bonding interactions between the μ-OH<sup>-</sup> bridging ligands and the O<sub>2</sub> adsorbate.</p>

Exchange-Biasing in a Dinuclear Dysprosium(III) Single-Molecule Magnet with a Large Energy Barrier for Magnetization Reversal

2019 ◽  
Author(s):  
Tian Han ◽  
Marcus J. Giansiracusa ◽  
Zi-Han Li ◽  
You-Song Ding ◽  
Nicholas F. Chilton ◽  
...  
Keyword(s):  
Single Molecule ◽  
Magnetization Reversal ◽  
Energy Barrier ◽  
Magnetic Hysteresis ◽  
Large Energy ◽  
Magnetic Studies ◽  
Bridging Ligands ◽  
Single Molecule Magnet ◽  
Exchange Biasing

A dichlorido-bridged dinuclear dysprosium(III) single-molecule magnet [Dy<sub>2</sub>L<sub>2</sub>(<i>µ</i>-Cl)<sub>2</sub>(THF)<sub>2</sub>] has been made using a diamine-bis(phenolate) ligand, H<sub>2</sub>L. Magnetic studies show an energy barrier for magnetization reversal (<i>U</i><sub>eff</sub>) around 1000 K. Exchange-biasing effect is clearly seen in magnetic hysteresis with steps up to 4 K. <i>Ab</i> initio calculations exclude the possibility of pure dipolar origin of this effect leading to the conclusion that super-exchange <i>via</i> the chloride bridging ligands is important.

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