Experimental and theoretical insights into the photomagnetic effects in trinuclear and ionic Cu(ii)–Mo(iv) systems

Abstract

The crystal engineering of octacyanidomolybdate(IV) ions and copper(II) complexes with two types of chelating ligands: multidentate blocking, tren = (tris(2 aminoethyl)amine, and bidentate capable of forming unusual organic bridges, tn...

Integration of Trinuclear Triangle Copper(II) Secondary Building Units in Octacyanidometallates(IV)-Based Frameworks

“…The experimental confirmation of the HOMO–LUMO gap further supports the analysis of magnetic data. It is also worth noting the calculated energy-level diagrams and frontier molecular orbitals for optimized [W­(CN) 8 ] 4– and [Mo­(CN) 8 ] 4– (Figures S10 and S12), which imply the diamagnetic nature of both components due to the presence of both spins on the same orbitals (61α,β) located on 5d x 2 – y 2 / z 2 and 4d x 2 – y 2 / z 2 orbitals of W and Mo, respectively …”

“…Additionally, considering both spin arrangements, the frontier molecular orbitals for [(TTC)­(CN) 3 ] (near the highest occupied molecular orbital, HOMO, and the lowest unoccupied molecular orbital, LUMO) are shown in Figures b and S11. For the model assuming total spin 1/2, the highest-energy spins (two α(↑) and one β­( ↓ )) were uniformly distributed between all 3d x 2 – y 2 orbitals of three square pyramidal Cu­(II) centers: HOMO­(121α), HOMO­(120β), and HOMO-1­(120α) . Interestingly, LUMO­(122α) and LUMO­(121β) were positioned on 3d x 2 – y 2 orbitals of only two Cu­(II) centers (Cu2 and Cu3), and LUMO + 1­(122β) was located on the 3d x 2 – y 2 orbital of the Cu1 center.…”

Crystal Engineering and Photomagnetic Studies of CN-Bridged Coordination Polymers Based on Octacyanidometallates(IV) and [Ni(cyclam)]2+

“…Moreover, for the first time we present the photomagnetic switching of octacyanidotungstate­(IV) and octacyanidomolybdate­(IV) photomagnetic chromophores embedded into the nickel­(II)-based coordination polymers ( 3 , 7 ). All previous examples involve other combinations of metal ions: Cu II –M IV (CN) 8 , , Zn II –M IV (CN) 8 , , Mn II –M IV (CN) 8 , , Fe II –M IV (CN) 8 , Cd II –M IV (CN) 8 , or Pt IV –M IV (CN) 8 (M = Mo, W). Similar to Mn II –M IV (CN) 8 coordination polymers, the photomagnetic response of M IV (CN) 8 moieties in the reported Ni II –M IV (CN) 8 frameworks is significantly stronger for the dehydrated phases as compared to the pristine ones.…”

Quantitative analysis of molecular surface: systematic application in the sodiation mechanism of a benzoquinone-based pillared compound as a cathode

“…In recent academic studies, Huan et al explored the lithiation process of the P5Q cathode based on density functional theory (DFT) for the first time. [25][26][27][28][29] All lithiated structures of P5Q were compared, and the lowest energy one was selected to predict the possible Li-binding site. However, it is time-consuming and some possible product structures could be neglected easily.…”