迟力峰院士、张海明教授及其合作者在J. Am. Chem. Soc.上发表论文

Substrate-Modulated Synthesis of Metal–Organic Hybrids by Tunable Multiple Aryl–Metal Bonds

作者：

Qigang Zhong^1,2,#, Kaifeng Niu^1,3,#, Long Chen^4,5,#, Haiming Zhang^1*, Daniel Ebeling², Jonas Björk³, Klaus Müllen^4,6, André Schirmeisen^2*, and Lifeng Chi^1*

单位：

¹Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Institute of Functional Nano & Soft Materials, Soochow University, 215123 Suzhou, China;

²Institute of Applied Physics, Justus-Liebig University Giessen, 35392 Giessen, Germany.

³Department of Physics, Chemistry and Biology, IFM, Linköping University, 58183 Linköping, Sweden.

⁴Max Planck Institute for Polymer Research, 55128 Mainz, Germany.

⁵State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, 130012 Changchun, China.

⁶Institute of Physical Chemistry, Johannes Gutenberg University Mainz, 55128 Mainz, Germany.

摘要：

Assembly of semiconducting organic molecules with multiple aryl−metal covalent bonds into stable one- and two-dimensional (1D and 2D) metal−organic frameworks represents a promising route to the integration of single-molecule electronics in terms of structural robustness and charge transport efficiency. Although various metastable organometallic frameworks have been constructed by the extensive use of single aryl−metal bonds, it remains a great challenge to embed multiple aryl−metal bonds into these structures due to inadequate knowledge of harnessing such complex bonding motifs. Here, we demonstrate the substrate-modulated synthesis of 1D and 2D metal−organic hybrids (MOHs) with the organic building blocks (perylene) interlinked solely with multiple aryl−metal bonds via the stepwise thermal dehalogenation of 3,4,9,10-tetrabromo-1,6,7,12-Tetrachloroperylene and subsequent metal−organic connection on metal surfaces. More importantly, the conversion from 1D to 2D MOHs is completely impeded on Au(111) but dominant on Ag(111). We comprehensively study the distinct reaction pathways on the two surfaces by visually tracking the structural evolution of the MOHs with high-resolution scanning tunneling and noncontact atomic force microscopy, supported by first-principles density functional theory calculations. The substrate-dependent structural control of the MOHs is attributed to the variation of the M−X (M = Au, Ag; X = C, Cl) bond strength regulated by the nature of the metal species.

影响因子：

15.419

分区情况：

一区

链接：

https://pubs.acs.org/doi/abs/10.1021/jacs.2c01338