Showing papers on "Spectrochemical series published in 2020"

Tunable Cobalt-Polypyridyl Catalysts Supported on Metal-Organic Layers for Electrochemical CO2 Reduction at Low Overpotentials.

Abstract: The Co center is active in electrochemical CO2 reduction (CO2RR), and its activity can be tuned by changing its coordination environment. However, the coordination number around the Co center cannot be readily changed in homogeneous systems owing to bimolecular decomposition of reduced low-coordinate Co species. Herein we report the systematic tuning of N atom numbers from 2 to 5 in the first coordination sphere around Co centers supported on two-dimensional metal-organic layers (MOLs) for the electrochemical CO2RR. The N atoms come from a combination of bipyridine, terpyridine, and phenylpyridine ligands. The Co centers are isolated and stabilized on the MOL to prevent bimolecular decomposition. All of the catalysts, denoted MOL-Co-Nx (x = 2-5), are active in reducing CO2 to CO electrochemically, but their activities are highly dependent on the number of coordinating N atoms. MOL-Co-N3 showed the highest current density of 2.3 A mg-1 with a CO Faradaic efficiency of 99% at an overpotential of only 380 mV. Density functional theory calculations attribute the high activity of the Co-N3 center to a balance of ligand field strength and open coordination site: the high ligand field strength promotes back-bonding, while the open coordination site allows HCO3- assistance, both of which accelerate C-O cleavage. MOLs thus provide a unique platform to systematically study the relationship between the coordination environment and the reactivity of open metal sites in electrocatalysis.

Effect of Ligand Field Strength on the Spin Crossover Behaviour in 5-X-SalEen (X=Me, Br and OMe) Based Fe(III) Complexes.

Abstract: The reaction of Fe(NCS)3 prepared in situ in MeOH with 5-X-SalEen ligands (5-X-SalEen=condensation product of 5-substituted salicylaldehyde and N-ethylethylenediamine) provided three Fe(III) complexes, [Fe(5-X-SalEen)2 ]NCS; X=Me (1), X=Br (2), X=OMe (3). All the complexes reveal similar structural features but a very different magnetic profile. Complex 1 shows a gradual spin crossover while complexes 2 and 3 show a sharp spin transition. The T1/2 for complex 2 is 237 K while for complex 3 it is much higher with a value of 361 K. The spin transition temperature is shifted towards higher temperature with increasing electron-donation ability of the ligand substituents. This experimental observation has been rationalized with DFT calculations. UV-Vis and cyclic voltammetry studies support the fact that the electron density on the ligand increases from Me to Br to OMe substituents. To understand the change in spin states, temperature-dependent EPR spectra have been recorded. The spin state equilibrium in the liquid state has been probed with Evans NMR spectroscopic method, and thermodynamic parameters have been evaluated for all complexes.

More efficient spin-orbit coupling: adjusting the ligand field strength to the second metal ion in asymmetric binuclear platinum(ii) configurations.

Abstract: Two types of asymmetric binuclear platinum(II) complexes (Pt-1 and Pt-3) bearing bridging ligands of 2-(2,4-difluorophenyl)-5-(pyridin-2-yl)pyridine and 2-(2,4-difluorophenyl)-4-(pyridin-2-yl)pyridine as well as their corresponding mononuclear counterparts (Pt-2, Pt-4, and Pt-5) were synthesized and characterized. Different chelating constructions of the second platinum(II) ions and the bridging ligands in Pt-1 and Pt-3 gave rise to two kinds of electron-transition pathway during their photophysical processes. The meta-/para-carbon of nitrogen on the center pyridyl segments set different levels of ligand field strength to the second platinum(II) ions, lowering their occupied d orbital to varying degrees. Pt-1 showed an enhanced spin–orbit coupling (SOC), caused by the additional metal component through direct orbital hybridization at higher states, where the fixed molecular skeleton induced by the additional metal–ligand bonding also helped to suppress molecular distortion in the excited state, ensuring a high quantum yield (Φ, 0.89 in toluene), which is among the best results in bimetallic complexes. While the second platinum(II) ion in Pt-3 seemed to make no contribution to the radiative transition, and only contributed to the HOMO, it provided a benefit by enlarging the conjugate system. Solution-processed organic lighting emitting devices (OLEDs) fabricated with the bimetallic Pt-1 emitter achieved superior efficiencies and up to 21% external quantum efficiency (EQE) in the Kelly-green region.