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Using a combination of two-dimensional infrared (2D IR) and variable temperature Fourier transform infrared (FTIR) spectroscopies the rapid structural isomerization of a five-coordinate ruthenium complex is investigated. In methylene chloride, three exchanging isomers were observed: (1) square pyramidal equatorial, ( 1 ); (2) trigonal bipyramidal, ( 0 ); and (3) square pyramidal apical, ( 2 ). Exchange between 1 and 0 was found to be an endergonic process (Δ H = 0.84 (0.08) kcal mol −1 , Δ S = 0.6 (0.4) eu) with an isomerization time constant of 4.3 (1.5) picoseconds (ps, 10 −12 s). Exchange between 0 and 2 however was found to be exergonic (Δ H = −2.18 (0.06) kcal mol −1 , Δ S = −5.3 (0.3) eu) and rate limiting with an isomerization time constant of 6.3 (1.6) ps. The trigonal bipyramidal complex was found to be an intermediate, with an activation barrier of 2.2 (0.2) kcal mol −1 and 2.4 (0.2) kcal mol −1 relative to the equatorial and apical square pyramidal isomers respectively. This study provides direct validation of the mechanism of Berry pseudorotation – the pairwise exchange of ligands in a five-coordinate complex – a process that was first described over fifty years ago. This study also clearly demonstrates that the rate of pseudorotation approaches the frequency of molecular vibrations. 

Organic‐based magnetic materials have been used for spintronic device applications as electrodes of spin aligned carriers and spin‐pumping substrates. Their advantages over more traditional inorganic magnets include reduced magnetic damping and lower fabrication costs. Vanadium tetracyanoethylene, V[TCNE]_x(x ≈ 2), is an organic‐based ferrimagnet with an above room‐temperature magnetic order temperature (T_c ≈ 400 K). V[TCNE]_xhas deposition flexibility and can be grown on a variety of substrates via low‐temperature chemical vapor deposition (CVD). A systematic study of V[TCNE]_xthin‐film CVD parameters to achieve optimal film quality, reproducibility, and excellent magnetic properties is reported. This is assessed by broadband ferromagnetic resonance (FMR) that shows most narrow linewidth of ≈1.5 Gauss and an extremely low Gilbert damping coefficient. The neat V[TCNE]_xfilms are shown to be efficient spin injectors via spin pumping into an adjacent platinum layer. Also, under an optimized FMR linewidth, the V[TCNE]_xfilms exhibit Fano‐type resonance with a continuum broadband absorption in the microwave range, which can be readily tuned by the microwave frequency.

 

Spin waves, quantized as magnons, have low energy loss and magnetic damping, which are critical for devices based on spin‐wave propagation needed for information processing devices. The organic‐based magnet [V(TCNE)_x; TCNE = tetracyanoethylene;x≈ 2] has shown an extremely low magnetic damping comparable to, for example, yttrium iron garnet (YIG). The excitation, detection, and utilization of coherent and non‐coherent spin waves on various modes in V(TCNE)_xis demonstrated and show that the angular momentum carried by microwave‐excited coherent spin waves in a V(TCNE)_xfilm can be transferred into an adjacent Pt layer via spin pumping and detected using the inverse spin Hall effect. The spin pumping efficiency can be tuned by choosing different excited spin wave modes in the V(TCNE)_xfilm. In addition, it is shown that non‐coherent spin waves in a V(TCNE)_xfilm, excited thermally via the spin Seebeck effect, can also be used as spin pumping source that generates an electrical signal in Pt with a sign change in accordance with the magnetization switching of the V(TCNE)_x. Combining coherent and non‐coherent spin wave detection, the spin pumping efficiency can be thermally controlled, and new insight is gained for the spintronic applications of spin wave modes in organic‐based magnets.