| Autor: |
Suryadevara N; Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Eggenstein-LeopoldshafenD-76344, Germany.; Institute for Quantum Materials and Technology (IQMT), Karlsruhe Institute of Technology (KIT), Eggenstein-LeopoldshafenD-76344, Germany., Boudalis AK; Institute for Quantum Materials and Technology (IQMT), Karlsruhe Institute of Technology (KIT), Eggenstein-LeopoldshafenD-76344, Germany.; Institut de Science et d'Ingénierie Suparamolaiculaires─ISIS, 8 allée Gaspard Monge, BP 70028, Strasbourg CedexF-67083, France.; Institut de Chimie de Strasbourg (UMR 7177, CNRS-Unistra), Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, StrasbourgF-67081, France., Olivares Peña JE; Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Eggenstein-LeopoldshafenD-76344, Germany., Moreno-Pineda E; Departamento de Química-Física, Facultad de Ciencias Naturales, Exactas y Tecnología, Universidad de Panamá, Panama0824, Panama., Fediai A; Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Eggenstein-LeopoldshafenD-76344, Germany., Wenzel W; Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Eggenstein-LeopoldshafenD-76344, Germany., Turek P; Institut de Chimie de Strasbourg (UMR 7177, CNRS-Unistra), Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, StrasbourgF-67081, France., Ruben M; Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Eggenstein-LeopoldshafenD-76344, Germany.; Institute for Quantum Materials and Technology (IQMT), Karlsruhe Institute of Technology (KIT), Eggenstein-LeopoldshafenD-76344, Germany.; Institut de Science et d'Ingénierie Suparamolaiculaires─ISIS, 8 allée Gaspard Monge, BP 70028, Strasbourg CedexF-67083, France. |
| Abstrakt: |
A mixed-ligand phthalocyanine/porphyrin yttrium(III) radical double-decker complex ( DD ) was synthesized using the custom-made 5,10,15-tris(4-methoxyphenyl)-20-(4-((trimethylsilyl)ethynyl)phenyl)porphyrin. The trimethylsilyl functionality was then used to couple two such complexes into biradicals through rigid tethers. Glaser coupling was used to synthesize a short-tethered biradical ( C1 ) and Sonogashira coupling to synthesize longer-tethered ones ( C2 and C3 ). Field-swept echo-detected (FSED), saturation recovery, and spin nutation-pulsed electron paramagnetic resonance experiments revealed marked similarities of the magnetic properties of DD with those of the parent [Y(pc) 2 ] • complex, both in the solid state and in CD 2 Cl 2 /CDCl 3 4:1 frozen glasses. FSED experiments on the biradicals C2 and C3 revealed a spectral broadening with respect to the spectra of DD and [Y(pc) 2 ] • assigned to the effect of dipolar interactions in solution. Apart from the main resonance, satellite features were also observed, which were simulated with dipole-dipole pairs of shortest distances, suggesting spin delocalization on the organic tether. FSED experiments on C1 yielded spectral line shapes that could not be simulated as the integration of the off-resonance echoes was complicated by field-dependent modulations. While, for all dimers, the on-resonance spin nutation experiments yielded Rabi oscillations of the same frequencies, off-resonance nutations on C1 yielded Rabi oscillations that could be assigned to a M S = -1 to M S = 0 transition within a S = 1 multiplet. The DFT calculations showed that the trans conformation of the complexes was significantly more stable than the cis one and that it induced a marked spin delocalization over the rigid organic tether. This "spin leakage" was most pronounced for the shortest biradical C1 . |
