Alexander Schnegg

The magnetic properties of pseudotetrahedral Co(II) complexes spawned intense interest after (PPh₄)₂[Co(SPh)₄] was shown to be the first mononuclear transition-metal complex displaying slow relaxation of the magnetization in the absence of a direct current magnetic field. However, there are differing reports on its fundamental magnetic spin Hamiltonian (SH) parameters, which arise from inherent experimental challenges in detecting large zero-field splittings. There are also remarkable changes in the SH parameters of [Co(SPh)₄]^2– upon structural variations, depending on the counterion and crystallization conditions. In this work, four complementary experimental techniques are utilized to unambiguously determine the SH parameters for two different salts of [Co(SPh)₄]^2–: (PPh₄)₂[Co(SPh)₄] (1) and (NEt₄)₂[Co(SPh)₄] (2). The characterization methods employed include multifield SQUID magnetometry, high-field/high-frequency electron paramagnetic resonance (HF-EPR), variable-field variable-temperature magnetic circular dichroism (VTVH-MCD), and frequency domain Fourier transform THz-EPR (FD-FT THz-EPR). Notably, the paramagnetic Co(II) complex [Co(SPh)₄]^2– shows strong axial magnetic anisotropy in 1, with D = −55(1) cm^–1 and E/D = 0.00(3), but rhombic anisotropy is seen for 2, with D = +11(1) cm^–1 and E/D = 0.18(3). Multireference ab initio CASSCF/NEVPT2 calculations enable interpretation of the remarkable variation of D and its dependence on the electronic structure and geometry.

THz Electron Paramagnetic Resonance / THz Spectroscopy at BESSY II

We present a comparison of experimental and simulated frequency- and field-domain electron paramagnetic resonance (EPR) spectra of integer and half-integer high-spin transition-metal ion complexes. For the simulation of EPR spectra a new tool within the EPR simulation software EasySpin is introduced, which allows for field- and frequency-domain EPR simulations with the same theoretical model and the same set of spin Hamiltonian parameters. The utility of this approach is demonstrated on the integer-spin complexes NiBr₂(PPh₃)₂ and [Tp₂Mn]SbF₆ (both S = 1) and the half-integer-spin Fe(III) porphyrins, hemin (Fe(PPIX)Cl) and Fe(TPP)Cl (both S = 5/2). We demonstrate that the combination of field- and frequency-domain EPR techniques allows the determination of spin Hamiltonian parameters, in particular large zero-field splittings, with high accuracy.

Here we describe a new high frequency/high field continuous wave and pulsed electrically detected magnetic resonance (CW EDMR and pEDMR) setup, operating at 263 GHz and resonance fields between 0 and 12 T. Spin dependent transport in illuminated hydrogenated amorphous silicon p-i-n solar cells at 5 K and 90 K was studied by in operando 263 GHz CW and pEDMR alongside with complementary X-band CW EDMR. Benefiting from the superior resolution at 263 GHz, we were able to better resolve EDMR signals originating from spin dependent hopping and recombination processes. 5 K EDMR spectra were found to be dominated by conduction and valence band tale states involved in spin dependent hopping, with additional contributions from triplet exciton states. 90 K EDMR spectra could be assigned to spin pair recombination involving conduction band tail states and dangling bonds as dominating spin dependent transport process, with additional contributions from valence band tail and triplet exciton states.