Intercluster exchange pathways in polymer-chain molecular magnets Cu(hfac)2L(R) unveiled by electron paramagnetic resonance.
Polymer-chain complexes Cu(hfac)(2)L(R) represent an interesting type of molecular magnets exhibiting thermally induced and light-induced magnetic switching, in many respects similar to a spin crossover. In the majority of these compounds the polymer chain consists of alternating one- and three-spin units composed of copper(II) ions and nitronyl nitroxides. The principal one-dimensional structure of the complexes has previously been assumed to play a key role in the observed magnetic anomalies. Using Q-band electron paramagnetic resonance (EPR) spectroscopy, we have reliably demonstrated that these complexes are indeed one-dimensional in the sense of the topology of their exchange channels; however, the magnetic chains spread across the structural polymer chains and consist solely of spin triads of nitroxide-copper(II)-nitroxide. Using four selected examples of complexes Cu(hfac)(2)L(R), we have found the exchange coupling values between spin triads of neighboring polymer chains to range from <1 to ca. 10 cm(-1). This conclusion could only be reached due to the selective probing of one- and three-spin units by EPR and correlates perfectly with both previous magnetic susceptibility data and quantum chemical calculations performed in this work. These findings give new insights into the cooperativity effects and mechanisms of magnetic anomalies in the Cu(hfac)(2)L(R) family of molecular magnets.
Fedin
Matvey V
MV
International Tomography Center SB RAS, Institutskaya str. 3a, 630090 Novosibirsk, Russia. mfedin@tomo.nsc.ru
Veber
Sergey L
SL
Maryunina
Ksenia Yu
KY
Romanenko
Galina V
GV
Suturina
Elizaveta A
EA
Gritsan
Nina P
NP
Sagdeev
Renad Z
RZ
Ovcharenko
Victor I
VI
Bagryanskaya
Elena G
EG
D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004578:Electron Spin Resonance Spectroscopy; D008024:Ligands; D008280:Magnetics; D008958:Models, Molecular; D056004:Molecular Dynamics Simulation; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D011108:Polymers / Q000737:chemistry*
D008024:Ligands; D009942:Organometallic Compounds; D011108:Polymers; D003300:Copper