Secondary Coordination Sphere Effects in Ruthenium(III) Tetraammine Complexes: Role of the Coordinated Water Molecule

2015 ◽  
Vol 54 (4) ◽  
pp. 2067-2080 ◽  
Author(s):  
Maykon L. Souza ◽  
Eduardo E. Castellano ◽  
Joshua Telser ◽  
Douglas W. Franco
Keyword(s):  
Water Molecule ◽  
Coordination Sphere ◽  
Secondary Coordination Sphere ◽  
Coordinated Water

scholarly journals The Role of the Secondary Coordination Sphere in a Fungal Polysaccharide Monooxygenase

2017 ◽  
Vol 12 (4) ◽  
pp. 1095-1103 ◽  
Author(s):  
Elise A. Span ◽  
Daniel L. M. Suess ◽  
Marc C. Deller ◽  
R. David Britt ◽  
Michael A. Marletta
Keyword(s):  
Coordination Sphere ◽  
Secondary Coordination Sphere ◽  
Polysaccharide Monooxygenase

Deciphering the role of anions and secondary coordination sphere in tuning anisotropy in Dy(III) air‐stable D5h SIMs

2021 ◽  
Author(s):  
Ramaswamy Murugavel ◽  
Sandeep K. Gupta ◽  
Sourav Dey ◽  
Thayalan Rajeshkumar ◽  
Gopalan Rajaraman
Keyword(s):  
Coordination Sphere ◽  
Secondary Coordination Sphere

The structure of {[Co(pht)(bpy)(H2O)]·3H2O} n (pht is phthalate and bpy is 4,4′-bipyridine) and the role of solvent water clusters in structure stability

2014 ◽  
Vol 70 (5) ◽  
pp. 440-444 ◽  
Author(s):  
Miguel Angel Harvey ◽  
Sebastián Suarez ◽  
Fabio Doctorovich ◽  
Fabio D. Cukiernik ◽  
Ricardo Baggio
Keyword(s):  
Hydrogen Bonds ◽  
Water Molecule ◽  
Coordination Polymers ◽  
Water Clusters ◽  
Structure Stability ◽  
Water Molecules ◽  
Solvent Water ◽  
Coordinated Water ◽  
Role Of Solvent

The CoII cation in poly[[aqua(μ-benzene-1,2-dicarboxylato-κ3 O 1,O 2:O 1)(μ-4,4′-bipyridine-κ2 N:N′)cobalt(II)] trihydrate], {[Co(C8H4O4)(C10H8N2)(H2O)]·3H2O} n , is octahedrally coordinated by two N atoms of two 4,4′-bipyridine ligands, three O atoms from phthalate anions and a fourth O atom from a coordinated water molecule. The packing consists of planes of coordination polymers linked by hydrogen bonds mediated by three solvent water molecules; the linkage is achieved by the water molecules forming intricate oligomeric clusters which also involve the O atoms of the phthalate ligands.

scholarly journals Deciphering the role of anions and secondary coordination sphere in tuning anisotropy in Dy(III) air-stable D5h SIMs

2021 ◽  
Author(s):  
Sandeep Gupta ◽  
Sourav Dey ◽  
Thayalan Rajeshkumar ◽  
Gopalan Rajaraman ◽  
Ramaswamy Murugavel
Keyword(s):  
High Temperature ◽  
Crystal Field ◽  
Coordination Sphere ◽  
Energy Barrier ◽  
Blocking Temperature ◽  
High Symmetry ◽  
Coordination Geometry ◽  
Secondary Coordination Sphere ◽  
Hydrogen Bonded

Precise control of the crystal field and symmetry around the paramagnetic spin centre has recently facilitated the engineering of high-temperature single-ion magnets (SIMs), the smallest possible units for future spin-based devices. In the present work, we report a series of air-stable seven coordinate Dy(III) SIMs {[L2Dy(H2O)5][X]3·L2·n(H2O), n = 0, X = Cl (1), n = 1, X = Br (2), I (3)} possessing pseudo-D5h symmetry or pentagonal bipyramidal coordination geometry with high anisotropy energy barrier (Ueff) and blocking temperature (TB). While the strong axial coordination from the sterically encumbered phosphonamide, tBuPO(NHiPr)2 (L), increases the overall anisotropy of the system, the presence of high symmetry significantly quenches quantum tunnelling of magnetization, which is the prominent deactivating factor encountered in SIMs. Although the local coordination geometry and the symmetry around the Dy(III) in all the three complexes are similar and display only slight deviations, the variation of halide anions in the secondary coordination sphere which is hydrogen-bonded to the coordinated equatorial water molecules, show subtle alteration in the magnetic properties. The energy barrier (Ueff) and the blocking temperature (TB) decrease in the order 3 > 2 > 1 with the change of anions from larger iodide to smaller strongly hydrogen-bonded chloride in the secondary coordination sphere. Ab initio CASSCF/RASSI-SO/SINGLE_ANISO calculations further provide deeper insights into the dynamics of magnetic relaxation in addition to the role of the secondary coordination sphere in modulating the anisotropy of the D5h systems, using diverse models. Thus, in addition to the importance of the crystal field and the symmetry to obtain high-temperature SIMs, this study also probes the significance of the secondary coordination sphere that can be tailored to accomplish novel SIMs.

Scrutinising the role of intramolecular hydrogen bonding in water exchange dynamics of Gd(III) complexes

2021 ◽  
Author(s):  
Loredana Leone ◽  
Sara Camorali ◽  
Antia Freire Garcia ◽  
Carlos Platas Iglesias ◽  
David Esteban ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Water Molecule ◽  
Water Exchange ◽  
Intramolecular Hydrogen Bonding ◽  
Coordinated Water ◽  
Intramolecular Hydrogen

We report a series of structurally related Gd(III) complexes designed to modulate the exchange of the coordinated water molecule, which is an important parameter to be controlled to achieve optimal...

scholarly journals Using internal electrostatic fields to manipulate the valence manifolds of copper complexes

2021 ◽  
Author(s):  
Alexander B. Weberg ◽  
Samuel P. McCollom ◽  
Laura M. Thierer ◽  
Michael R. Gau ◽  
Patrick J. Carroll ◽  
...  
Keyword(s):  
Coordination Sphere ◽  
Copper Complexes ◽  
Photophysical Properties ◽  
Redox Potentials ◽  
Electrostatic Effects ◽  
Electrostatic Fields ◽  
Secondary Coordination Sphere

Secondary coordination sphere electrostatic effects tune the valence manifolds of copper centers, impacting molecular geometries, photophysical properties, and redox potentials.

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