Conformational Tuning of Magnetic Interactions in Coupled Nanographenes

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2024-09-30 DOI:10.1021/acs.nanolett.4c03518

Gonçalo Catarina, Elia Turco, Nils Krane, Max Bommert, Andres Ortega-Guerrero, Oliver Gröning, Pascal Ruffieux, Roman Fasel, Carlo A. Pignedoli

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Abstract

Phenalenyl (C₁₃H₉) is an open-shell spin-1/2 nanographene. Using scanning tunneling microscopy (STM) inelastic electron tunneling spectroscopy (IETS), covalently bonded phenalenyl dimers have been shown to feature conductance steps associated with singlet–triplet excitations of a spin-1/2 dimer with antiferromagnetic exchange. Here, we address the possibility of tuning the magnitude of the exchange interactions by varying the dihedral angle between the two molecules within a dimer. Theoretical methods ranging from density functional theory calculations to many-body model Hamiltonians solved within different levels of approximation are used to explain STM-IETS measurements of phenalenyl dimers on a hexagonal boron nitride (h-BN)/Rh(111) surface, which exhibit signatures of twisting. By means of first-principles calculations, we also propose strategies to induce sizable twist angles in surface-adsorbed phenalenyl dimers via functional groups, including a photoswitchable scheme. This work paves the way toward tuning magnetic couplings in carbon-based spin chains and two-dimensional lattices.

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耦合纳米石墨烯中磁性相互作用的构象调谐

苯戊烯（C13H9）是一种开壳自旋-1/2 纳米锗。利用扫描隧道显微镜（STM）非弹性电子隧道光谱（IETS），共价键合的苯丙烯基二聚体被证明具有与自旋-1/2 二聚体的单三重激发和反铁磁交换相关的电导阶跃。在此，我们探讨了通过改变二聚体中两个分子之间的二面角来调整交换相互作用大小的可能性。从密度泛函理论计算到在不同近似水平下求解的多体模型哈密顿，这些理论方法都被用来解释在六方氮化硼（h-BN）/Rh(111)表面上对苯亚甲基二聚体进行的 STM-IETS 测量。通过第一原理计算，我们还提出了通过官能团诱导表面吸附的苯亚甲基二聚体产生可观扭转角的策略，包括一种光开关方案。这项工作为调整碳基自旋链和二维晶格中的磁耦合铺平了道路。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.