Magnetic dimeric metal–porphyrin rings mechanically bonded around carbon nanotubes: the role of nanotube defects modulating magnetic properties

Abstract

Carbon nanotubes constitute an excellent option to connect molecular nanomagnets (MNMs) to solid-state devices, allowing the electrical control of the molecule spin state. The main challenge in this area is to obtain stable nanohybrid structures that preserve the magnetic properties and functionality of the molecule. One of the strategies developed to build these structures combining MNMs and carbon nanotubes involves the encapsulation of the nanotube within magnetic organic macrocycle(s), leading to magnetic mechanically interlocked derivatives of carbon nanotubes (mMINTs). Recently, mMINTs with dimeric metal–porphyrin rings containing Cu²⁺ or Co²⁺ attached to carbon nanotubes have been synthesized. Different structural and spectroscopic techniques confirm that the metal centers in both mMINTs preserve the coordination sphere and structure of the free macrocycles, with only small deviations from the square planar geometry. However, different magnetic behaviors are observed depending on the metal. The Cu derivative has well-preserved spin geometry, with quantum coherence times on the microsecond scale, as in the free molecule (τ = 25 μs). In contrast, the continuous-wave electron paramagnetic resonance (EPR) spectrum measured on the Co derivative does not show any clear contribution from Co, although EXAFS unambiguously shows the presence of Co²⁺. In order to understand this different magnetic behavior, we studied mMINTs by means of periodic DFT calculations. The analysis of the optimized geometries, the spin density of the free macrocycles and the mMINTs, the adsorption energies, the extension of the charge transfer between the macrocycle and the nanotube and the density of states reveals a stronger macrocycle–nanotube interaction for the Co-mMINT. Our results point to carbon vacancies in the nanotubes as responsible for the different macrocycle–nanotube interaction and the observed loss of the Co²⁺ EPR signal in the Co-mMINT.