Diverse Superatomic Magnetic and Spin Properties of Au144(SC8H9)60 Clusters

IF 10.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

ACS Central Science Pub Date : 2025-05-29 DOI:10.1021/acscentsci.5c00139

Juniper Foxley, Marcus Tofanelli, Jane A. Knappenberger, Christopher J. Ackerson and Kenneth L. Knappenberger Jr.*,

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引用次数: 0

Abstract

Au₁₄₄(SC₈H₉)₆₀, a colloidal cluster with a 1.7 nm inorganic diameter, exhibits both metallic and molecular-like behavior, along with a distribution of unfilled superatom states. Its 1.7–2.5 eV electronic transitions were probed with variable-temperature, variable-field magnetic circular dichroism (VTV $\overset{⇀}{H}$ -MCD), revealing two energy regions with distinct responses. Below 2.0 eV, MCD transitions exhibited diverse VTV $\overset{⇀}{H}$ responses, including both paramagnetic and diamagnetic behavior, implicating multiple nondegenerate initial states originating within the open-shell superatom S, D, and H HOMO manifold. Above 2.0 eV, uniform field-dependent responses suggested spin-vibronic coupling due to metal–ligand mixing. The Au₁₄₄(SC₈H₉)₆₀ magneto-optical response is surprisingly complex given the system’s high electronic-state density; discrete structural domains of the cluster, including the superatomic metal core, likely contribute to this diversity. These results show the potential to investigate and tailor the magneto-optical and spin properties of these clusters through structurally precise synthesis and also identify superatomic colloids as candidates for advancing spin-based technologies.

Superatom spin properties of structurally precise gold clusters are resolved using magnetic field spectroscopy. Evidence of high-angular-momenta H superatoms and paramagnetic centers is revealed.

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Au144(SC8H9)60团簇的超原子磁性和自旋特性

Au144(SC8H9)60是一种无机直径为1.7 nm的胶体团簇，具有金属和分子样行为，并具有未填充的超原子态分布。用变温变场磁圆二色性（VTVH -MCD）探测了其1.7 ~ 2.5 eV的电子跃迁，发现了两个具有不同响应的能量区。在2.0 eV以下，MCD跃迁表现出不同的VTVH响应，包括顺磁性和反磁性行为，这意味着在开壳超原子S、D和H HOMO流形中产生了多个非简并初始态。在2.0 eV以上，均匀的场相关响应表明由于金属配体混合导致的自旋振动耦合。考虑到系统的高电子态密度，Au144(SC8H9)60磁光响应异常复杂；星团的离散结构域，包括超原子金属核心，可能有助于这种多样性。这些结果显示了通过结构精确合成来研究和定制这些团簇的磁光和自旋特性的潜力，并确定了超原子胶体作为推进自旋技术的候选者。利用磁场波谱分析了结构精密金团簇的超原子自旋性质。揭示了高角动量H超原子和顺磁中心的证据。

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来源期刊

ACS Central Science Chemical Engineering-General Chemical Engineering

CiteScore

25.50

自引率

0.50%

发文量

194

审稿时长

10 weeks

期刊介绍： ACS Central Science publishes significant primary reports on research in chemistry and allied fields where chemical approaches are pivotal. As the first fully open-access journal by the American Chemical Society, it covers compelling and important contributions to the broad chemistry and scientific community. "Central science," a term popularized nearly 40 years ago, emphasizes chemistry's central role in connecting physical and life sciences, and fundamental sciences with applied disciplines like medicine and engineering. The journal focuses on exceptional quality articles, addressing advances in fundamental chemistry and interdisciplinary research.