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南京大学向菲菲《Natl. Sci. Rev.》:Au (111) 上开壳层 [3] 三角烯稠合卟啉的表面合成与界面电荷重分布

  • 2026-04-10 05:49:10
南京大学向菲菲《Natl. Sci. Rev.》:Au (111) 上开壳层 [3] 三角烯稠合卟啉的表面合成与界面电荷重分布

开壳层碳基纳米结构在金属表面上的界面电荷转移,如何在分子尺度上调控其自旋态,并影响其前沿轨道的多体特性,一直是分子自旋电子学中的核心问题。近日,南京大学联合欧洲多家科研团队,设计并构建了一类全新的卟啉稠合纳米石墨烯杂化结构。通过精确的实验表征与理论计算,系统揭示了界面电荷转移对分子磁性与电子结构的调控机制。相关成果以“On-Surface Synthesis and Interfacial Charge Redistribution of Open-Shell [3]Triangulene-Fused Porphyrins on Au(111)”为题,发表于National Science Review

西班牙马德里自治大学的Miguel Martínez García与南京大学先进制造学院向菲菲副教授为论文共同第一作者;向菲菲副教授与捷克科学院Pavel Jelínek教授、马德里自治大学Tomas Torres教授和Giovanni Bottari教授为共同通讯作者。瑞士联邦材料与科学研究所Roman Fasel教授及其团队对本工作提供了重要指导,并在实验及部分理论计算方面给予了有力支持。

从三角型石墨烯到卟啉杂化体系
近年来,具有开壳层电子结构的石墨烯纳米结构(nanographene)因其弱自旋轨道耦合与潜在的长自旋相干时间,成为分子自旋电子学与量子材料研究的重要候选体系。其中,[3]triangulene作为一种典型的三角形石墨烯片段,天然具有两个未成对π电子,是研究分子磁性的理想平台。另一方面,卟啉分子因其稳定的共轭结构以及可嵌入过渡金属的能力,被广泛应用于功能分子设计中。如果能够将三角石墨烯单元与卟啉骨架共价融合,便有望构建出同时具备π电子磁性与结构可调性的复杂分子体系。基于这一思路,团队设计并合成了两类模型分子:含两个和四个三角石墨烯单元的,具有二重对称性的ZnPorT2,和具有四重对称性的ZnPorT4
一种简单却关键的实验策略
在表面合成过程中,一个长期存在的问题是分子的扩散与不受控的交联反应,这往往导致目标结构产率较低。为了解决这一问题,团队提出了一种“快速退火”(flash annealing)策略:先在室温沉积分子前驱体,再以较高升温速率迅速加热至反应温度,并在短时间内完成分子内脱氢环化反应过程。这一策略显著缩短了分子在表面的扩散时间,从而有效抑制了分子之间的交联反应,使目标产物ZnPorT2的产率从约5%提升至24%
图1 ZnPorT2的不同表面在位化学合成路径对其产物产率的影响,以及主要产物的化学结构表征
一个电子的转移,改变一切
在获得目标结构后,团队进一步利用低温扫描隧道显微镜与谱学技术STM/STS,结合密度泛函理论与多体计算,对其电子结构进行了系统研究。对于ZnPorT2分子,其本征状态为反铁磁耦合的双自由基diradical构型。当其吸附在Au(111)表面后,分子向衬底转移一个电子,形成带正电的ZnPorT2•+。尽管发生了电荷转移,该体系仍然保留一个未成对电子,维持开壳层磁性状态。相比之下,ZnPorT4则表现出截然不同的行为。该分子同样在本征态下具有反铁磁耦合的双自由基基态,但在吸附于金属表面后,其向衬底转移两个电子,最终形成的ZnPorT42+呈现出闭壳层结构构型。
图2 ZnPorT2的电子结构表征以及基于CASCI的Dyson轨道模拟
图3 ZnPorT4的电子结构表征以及基于CASCIDyson轨道模拟
超越单电子理论多体效应的必要性
值得注意的是,这类开壳层体系通常具有显著的多参考(multireference)特征,即其电子态无法由单一Slater行列式描述。因此,传统的DFT方法在某些情况下难以准确再现实验观测。为此,团队引入了多体理论方法,包括CASSCFCASCI计算,并进一步利用Dyson轨道来模拟扫描隧道谱图。计算结果与实验dI/dV图像高度一致,证明即使在发生电荷转移后,ZnPorT2体系仍然保留其多体电子结构特征。此外,在ZnPorT2中还观察到低能谱结构异常的现象。结合理论分析,团队提出该体系可能处于混合价态(mixed-valence)区域,其中电子在不同电荷态之间发生快速涨落。这种动态过程会削弱典型的Kondo特征,使体系表现出不同于传统局域自旋模型的行为。
对称性与电子结构的深层联系
ZnPorT2ZnPorT4之间的差异还揭示了几何对称性的重要作用。ZnPorT2具有较低对称性,其未成对电子主要分布在分子两端;而ZnPorT4具有更高的四重对称性,使得多个边缘态在能量上接近甚至简并。在理想情况下,可能导致电子态的竞争甚至产生自旋“阻挫”。然而,在实际实验中,界面电荷转移提供了一种替代的稳定机制,使ZnPorT4通过电子重新分布直接进入闭壳层状态,从而避免了对称性破缺带来的复杂行为。
图4 限制性Kohn-Sham计算获得的ZnPorT2与ZnPorT4的前沿轨道能级分布情况
展望
这项工作为未来分子自旋器件的设计提供了一个可能的方向。如果磁性可以通过界面电荷转移进行调控,那么通过调节衬底与分子的相互作用,便有可能实现对单分子自旋态的可控操纵。此外,卟啉结构所提供的金属配位位点,也为引入π–d电子耦合提供了新的可能性,从而进一步拓展体系的功能性。这类卟啉-纳米石墨烯杂化体系将在分子自旋电子学、有机量子比特以及原子尺度信息处理等领域展现出广阔的应用前景。
论文链接:
https://doi.org/10.1093/nsr/nwag155
点击文末“阅读原文”可直接访问

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    文章来源 | 向菲菲课题组

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  1. CONNECT:[ UseTime:0.000823s ] mysql:host=127.0.0.1;port=3306;dbname=b460;charset=utf8mb4
  2. SHOW FULL COLUMNS FROM `fenlei` [ RunTime:0.000911s ]
  3. SELECT * FROM `fenlei` WHERE `fid` = 0 [ RunTime:0.000369s ]
  4. SELECT * FROM `fenlei` WHERE `fid` = 63 [ RunTime:0.000345s ]
  5. SHOW FULL COLUMNS FROM `set` [ RunTime:0.000524s ]
  6. SELECT * FROM `set` [ RunTime:0.000224s ]
  7. SHOW FULL COLUMNS FROM `article` [ RunTime:0.000608s ]
  8. SELECT * FROM `article` WHERE `id` = 526874 LIMIT 1 [ RunTime:0.000761s ]
  9. UPDATE `article` SET `lasttime` = 1775958759 WHERE `id` = 526874 [ RunTime:0.001494s ]
  10. SELECT * FROM `fenlei` WHERE `id` = 65 LIMIT 1 [ RunTime:0.000713s ]
  11. SELECT * FROM `article` WHERE `id` < 526874 ORDER BY `id` DESC LIMIT 1 [ RunTime:0.001169s ]
  12. SELECT * FROM `article` WHERE `id` > 526874 ORDER BY `id` ASC LIMIT 1 [ RunTime:0.001142s ]
  13. SELECT * FROM `article` WHERE `id` < 526874 ORDER BY `id` DESC LIMIT 10 [ RunTime:0.004415s ]
  14. SELECT * FROM `article` WHERE `id` < 526874 ORDER BY `id` DESC LIMIT 10,10 [ RunTime:0.002852s ]
  15. SELECT * FROM `article` WHERE `id` < 526874 ORDER BY `id` DESC LIMIT 20,10 [ RunTime:0.003754s ]
0.179043s