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

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

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

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.

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.

The critical role of the coordination sphere in the high-efficiency blue-light emission from aminopyrazine metal-organic polymers

2021 ◽  
Vol 186 ◽  
pp. 109025
Author(s):  
João Humberto Dias Campos ◽  
Meiry Edivirges Alvarenga ◽  
Maykon Alves Lemes ◽  
José Antônio do Nascimento Neto ◽  
Freddy Fernandes Guimarães ◽  
...  
Keyword(s):  
Blue Light ◽  
Coordination Sphere ◽  
High Efficiency ◽  
Light Emission ◽  
Critical Role ◽  
Organic Polymers ◽  
Blue Light Emission ◽  
Metal Organic
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