By virtue of multitunable spin structures upon designing the π-electron topologies, phenalenyl-based nanographenes are of substantial interest in fundamental science and for potential applications in spintronics. Heptauthrene, as one of the well-known phenalenyl diradicals, is composed of one benzene-fused bisphenalenyls in mirror symmetry and expected to have a triplet ground state. However, the synthesis of unsubstituted heptauthrene remains very challenging due to the high reactivity of triplet diradicals. Here, we report a combined in-solution and on-surface synthesis of unsubstituted heptauthrene, whose chemical structure is characterized through bond-resolved atomic force microscopy. Combined with mean-field Hubbard model calculations, its triplet ground state is unambiguously confirmed by the underscreened Kondo resonance in response to the magnetic field, as well as the engineered spin-state switching upon extra hydrogen atom addition and dissociation on the radical site. Our results provide access to phenalenyl-based nanographenes with high-spin ground state, potentially useful in constructing high-spin networks.
Quantum nanomagnets exhibit collective quantum behaviors beyond the usual long range ordered states due to the interplay of low dimension, competing interactions and strong quantum fluctuations. Despite numerous theoretical works treating quantum magnetism, the experimental study of individual quantum nanomagnets remains very challenge, greatly hindering the development of this cutting-edge field. Here, we demonstrate an effective strategy to realize individual quantum nanomagnets in metal-free porphyrins by using combined onsurface synthesis and atom manipulation approaches, with the ultimate ability to arrange coupled spins one by one as envisioned by Richard Feynman 60 years ago. A series of metalfree porphyrin nanomagnets have been constructed on Au(111) and their collective magnetic properties have been thoroughly characterized on the atomic scale by scanning probe microscopy together with theoretical calculations. Our results reveal that the constructed S=1/2 antiferromagnets host a gapped excitation in consistent with isotropic Heisenberg antiferromagnets S=1/2 model, while the S=1 antiferromagnets with odd-number units exhibit two zero-mode end states due to quantum fluctuations. Our achieved strategy not only provides a unique testing bed to study the strongly correlated effects of quantum magnetism in purely organic materials, but expands the functionalities of porphyrins with implications for quantum technological applications.
Triangulene and its homologues are of considerable interest for molecular spintronics due to their high-spin ground states as well as the potential for constructing high spin frameworks. Realizing triangulene-based high-spin system on surface is challenging but of particular importance for understanding π-electron magnetism. Here, we report two approaches to generate triangulene trimers on Au(111) by using surface-assisted dehydration and alkyne trimerization, respectively. We find that the developed dehydration reaction shows much higher chemoselectivity thus resulting in significant promotion of product yield compared to that using alkyne trimerization approach, through cutting the side reaction path. Combined with spin-polarized density functional theory calculations, scanning tunneling spectroscopy measurements identify the septuple (S = 3) high-spin ground state and quantify the collective ferromagnetic interaction among three triangulene units. Our results demonstrate the approaches to fabricate high-quality triangulene-based high spin systems and understand their magnetic interactions, which are essential for realizing carbon-based spintronic devices.
Open-shell nanographenes appear as promising candidates for future applications in spintronics and quantum technologies. A critical aspect to realize this potential is to design and control the magnetic exchange. Here, we reveal the effects of frontier orbital symmetries on the magnetic coupling in diradical nanographenes through scanning probe microscope measurements and different levels of theoretical calculations. In these open-shell nanographenes, the exchange energy exhibits a remarkable variation between 20 and 160 meV. Theoretical calculations reveal that frontier orbital symmetries play a key role in affecting the magnetic coupling on such a large scale. Moreover, a triradical nanographene is demonstrated for investigating the magnetic interaction among three unpaired electrons with unequal magnetic exchange, in agreement with Heisenberg spin model calculations. Our results provide insights into both theoretical design and experimental realization of nanographene materials with different exchange interactions through tuning the orbital symmetry, potentially useful for realizing magnetically operable graphene-based nanomaterials.
Open-shell nanographenes appear as promising candidates for future applications in spintronics and quantum technologies. How to engineer and obtain large magnetic exchange coupling in nanographenes is crucial for realizing their applications at room temperature. Here, we reveal a mechanism of engineering magnetic exchange coupling in nanographenes through tailoring their frontier orbital symmetries, investigated by combining scanning probe microscope measurements and different levels of theoretical calculations. In nanographenes of phenalenyl spin dimers, their exchange interaction can be widely tuned from 20 meV to 160 meV. Theoretical calculations reveal that frontier orbital symmetries play a key role in engineering magnetic exchange coupling on such a large scale. Moreover, a spin trimer is demonstrated for investigating the magnetic interaction among three spins with unequal magnetic exchange coupling, in agreement with Heisenberg spin chain model calculations. Our results provide insights into both theoretical design and experimental realization of nanographene materials with widely tunable exchange interactions, potentially useful for realizing magnetically operable graphene nanomaterials.
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