Kladnik Gregor, Schio Luca, Bavdek Gregor, Tanuma Yuri, van Midden Mavrič Marion, Zupanič Erik, Anézo Bastien, Sideri Ioanna K, Tagmatarchis Nikos, Volkmann Jannis, Wegner Hermann A, Goldoni Andrea, Ewels Christopher P, Morgante Alberto, Floreano Luca, Arčon Denis, Cvetko Dean
Faculty of Mathematics and Physics, University of Ljubljana, Ljubljana, Slovenia.
CNR-IOM, Istituto Officina dei Materiali, Basovizza Area Science Park, Trieste, Italy.
Nat Commun. 2025 Jan 2;16(1):193. doi: 10.1038/s41467-024-55521-2.
We present an efficient strategy for on-surface engineering of organic metal-free supramolecular complexes with long-term spin protection. By vacuum deposition of azafullerene (CN) monomers on a pre-deposited template layer of [10]cycloparaphenylene ([10]CPP) nanohoops on Au(111) surface we exploit the molecular shape matching between the CN and [10]CPP for the azafullerene encapsulation with nanohoops in a guest-host complexation geometry. CN⊂[10]CPP supramolecular complexes self-assemble into an extended two-dimensional hexagonal lattice yielding a high density network of stable spin-1/2 radicals. We find compelling evidence for electronic coupling between the guest CN and the host [10]CPP in supramolecular species. At the same time, [10]CPP effectively protects the radical state of encapsulated azafullerenes against dimerization and inhibits CN coupling to the Au substrate. Azafullerene encapsulation by nanohoops represents a viable realization of molecular spin protection while simultaneously demonstrating exceptional self-assembling properties by which large-scale 2D architectures of molecular spins can be realized.
我们提出了一种高效的策略，用于在表面上构建具有长期自旋保护功能的无有机金属超分子配合物。通过在金（111）表面预先沉积的[10]环对亚苯基（[10]CPP）纳米环模板层上真空沉积氮杂富勒烯（CN）单体，我们利用CN与[10]CPP之间的分子形状匹配，以客体-主体络合几何结构将氮杂富勒烯封装在纳米环中。CN⊂[10]CPP超分子配合物自组装成扩展的二维六边形晶格，形成稳定的自旋1/2自由基的高密度网络。我们发现了超分子物种中客体CN与主体[10]CPP之间电子耦合的有力证据。同时，[10]CPP有效地保护了被封装氮杂富勒烯的自由基状态，防止其二聚化，并抑制CN与金基底的耦合。纳米环对氮杂富勒烯的封装代表了分子自旋保护的一种可行实现方式，同时展示了卓越的自组装特性，通过这些特性可以实现分子自旋的大规模二维结构。
