On the Spin-State Dependence of Redox Potentials of Spin Crossover Complexes

Abstract

Resistance switching properties of nanoscale junctions of spin crossover molecules have received recently much interest. In many cases, this property has been traced back to the variation of molecular orbital energies upon the spin transition. However, one can also expect a substantial reorganization of the molecular structure due to charge localization, which calls for a

Enhancement of spin Seebeck effect of reverse spin crossover Fe (II) micellar charge transport using PMMA polymer electrolyte

“…The reasons are lower energy gap and more unpair electrons of HS than LS. This was in agreement with the trend of energy gap that observed in the previous DFT simulation in Figure 6 and electrochemical band gap analysis [30] in Figure 9, where the HS state produce lower LUMO‐HOMO gap than LS state. Thus, the spin Seebeck observed after hot temperature of 313 K and above was inferred due to a decrease of G2 diffusion and significantly changes of electrochemical band gap.…”

Electrocatalytic Hydrogen Evolution by Cobalt Complexes with a Redox Non-Innocent Polypyridine Ligand

“…In the former redox process, the PPh 3 ligand exhibits more π-acceptor character than a DMF ligand and facilitates the reduction, − whereas in the latter redox process, the PPh 3 ligand shows mainly character of a σ donor and hinders electron transfer to the complex. Meanwhile, the different spin states of [Co­(ppq)­PPh 3 ] + and [Co­(ppq)­DMF] + (Table ) may influence oxidation or reduction potentials of these intermediates …”

“…Meanwhile, the different spin states of [Co(ppq)PPh 3 ] + and [Co(ppq)DMF] + (Table 1) may influence oxidation or reduction potentials of these intermediates. 41 The spin population and charge value analysis via DFT calculation (Tables 1 and S7) provides insights about the electronic structures of dominant Co-containing intermediates (DMF-bound) in the designated redox sequence of 1 and 2 (Figure 3b). The ground state of penta-coordinated [Co II (ppq)DMF] 2+ is found to be quartet (Figure S28), same as the measured high-spin state of [Co II (ppq)Cl 2 ].…”

Bidentate Pyridyl‐NHC Ligands: Synthesis, Ground and Excited State Properties of Their Iron(II) Complexes and the Role of the fac/mer Isomerism

“…In this context, insights provided by molecular modeling and simulations have all their attractiveness and importance. Traditionally, computational methods have been used to predict structures, describe spin-crossover phenomena, [77][78][79] predict electrochemical properties, [80,81] rationalize optical properties, [60,[82][83][84][85][86] and elucidate the nature and relative alignment of MLCT and MC states and the barriers for their mutual interconversion. [87,88] The large size of the iron-organic complexes often imposes the use of DFT and TD-DFT as methods of choice for tackling this problem, although the development and use of other methodologies derived from multiconfigurational approaches (sometimes in combination with DFT, as in hybrid DFT/wavefunction formalisms) is growing in the last years.…”