Non-covalent control of spin-state in metal-organic complex by positioning on N-doped graphene

作者：de la Torre Bruno; Svec Martin; Hapala Prokop; Redondo Jesus; Krejci Ondrej; Lo Rabindranath; Manna Debashree; Sarmah Amrit; Nachtigallova Dana; Tucek Jiri; Blonski Piotr; Otyepka Michal; Zboril Radek^*; Hobza Pavel^*; Jelinek Pavel^*

来源：Nature Communications, 2018, 9(1): 2831.

DOI：10.1038/s41467-018-05163-y

Nitrogen doping of graphene significantly affects its chemical properties, which is particularly important in molecular sensing and electrocatalysis applications. However, detailed insight into interaction between N-dopant and molecules at the atomic scale is currently lacking. Here we demonstrate control over the spin state of a single iron(II) phthalocyanine molecule by its positioning on N-doped graphene. The spin transition was driven by weak intermixing between orbitals with z-component of N-dopant (p(z) of N-dopant) and molecule (d(xz), d(yz), d(z)(2)) with subsequent reordering of the Fe d-orbitals. The transition was accompanied by an electron density redistribution within the molecule, sensed by atomic force microscopy with CO-functionalized tip. This demonstrates the unique capability of the high-resolution imaging technique to discriminate between different spin states of single molecules. Moreover, we present a method for triggering spin state transitions and tuning the electronic properties of molecules through weak non-covalent interaction with suitably functionalized graphene.

• 出版日期2018-7-19