Selective On-surface Covalent Coupling Based on Metal-organic Coordination Template

Overview

Journal Nat Commun

Specialty Biology

Date 2019 Jan 10

PMID 30622253

Citations 12

Authors

Shuaipeng Xing

Zhe Zhang

Xiyu Fei

Wei Zhao

Ran Zhang

Tao Lin

Danli Zhao

Huanxin Ju

Hu Xu

Jian Fan

Junfa Zhu

Yu-Qiang Ma

Ziliang Shi

Affiliations

Soon will be listed here.

Abstract

Control over on-surface reaction pathways is crucial but challenging for the precise construction of conjugated nanostructures at the atomic level. Herein we demonstrate a selective on-surface covalent coupling reaction that is templated by metal-organic coordinative bonding, and achieve a porous nitrogen-doped carbon nanoribbon structure. In contrast to the inhomogeneous polymorphic structures resulting from the debrominated aryl-aryl coupling reaction on Au(111), the incorporation of an Fe-terpyridine (tpy) coordination motif into the on-surface reaction controls the molecular conformation, guides the reaction pathway, and finally yields pure organic sexipyridine-p-phenylene nanoribbons. Emergent molecular conformers and reaction products in the reaction pathways are revealed by scanning tunneling microscopy, density functional theory calculations and X-ray photoelectron spectroscopy, demonstrating the template effect of Fe-tpy coordination on the on-surface covalent coupling. Our approach opens an avenue for the rational design and synthesis of functional conjugated nanomaterials with atomic precision.

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References

Otero G, Biddau G, Sanchez-Sanchez C, Caillard R, Lopez M, Rogero C . Fullerenes from aromatic precursors by surface-catalysed cyclodehydrogenation. Nature. 2008; 454(7206):865-8. DOI: 10.1038/nature07193. View

Kosynkin D, Higginbotham A, Sinitskii A, Lomeda J, Dimiev A, Price B . Longitudinal unzipping of carbon nanotubes to form graphene nanoribbons. Nature. 2009; 458(7240):872-6. DOI: 10.1038/nature07872. View

Llinas J, Fairbrother A, Borin Barin G, Shi W, Lee K, Wu S . Short-channel field-effect transistors with 9-atom and 13-atom wide graphene nanoribbons. Nat Commun. 2017; 8(1):633. PMC: 5608806. DOI: 10.1038/s41467-017-00734-x. View

Liu W, Luo X, Bao Y, Liu Y, Ning G, Abdelwahab I . A two-dimensional conjugated aromatic polymer via C-C coupling reaction. Nat Chem. 2017; 9(6):563-570. DOI: 10.1038/nchem.2696. View

Grimme S, Antony J, Ehrlich S, Krieg H . A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J Chem Phys. 2010; 132(15):154104. DOI: 10.1063/1.3382344. View

Sun Q, Cai L, Wang S, Widmer R, Ju H, Zhu J . Bottom-Up Synthesis of Metalated Carbyne. J Am Chem Soc. 2016; 138(4):1106-9. DOI: 10.1021/jacs.5b10725. View

Cai J, Pignedoli C, Talirz L, Ruffieux P, Sode H, Liang L . Graphene nanoribbon heterojunctions. Nat Nanotechnol. 2014; 9(11):896-900. DOI: 10.1038/nnano.2014.184. View

Sun Q, Zhang C, Li Z, Kong H, Tan Q, Hu A . On-surface formation of one-dimensional polyphenylene through Bergman cyclization. J Am Chem Soc. 2013; 135(23):8448-51. DOI: 10.1021/ja404039t. View

Urgel J, Hayashi H, Giovannantonio M, Pignedoli C, Mishra S, Deniz O . On-Surface Synthesis of Heptacene Organometallic Complexes. J Am Chem Soc. 2017; 139(34):11658-11661. DOI: 10.1021/jacs.7b05192. View

10.

Lin T, Shang X, Adisoejoso J, Liu P, Lin N . Steering on-surface polymerization with metal-directed template. J Am Chem Soc. 2013; 135(9):3576-82. DOI: 10.1021/ja311890n. View

11.

Constable E . 2,2':6',2''-terpyridines: from chemical obscurity to common supramolecular motifs. Chem Soc Rev. 2007; 36(2):246-53. DOI: 10.1039/b601166g. View

12.

Lafferentz L, Eberhardt V, Dri C, Africh C, Comelli G, Esch F . Controlling on-surface polymerization by hierarchical and substrate-directed growth. Nat Chem. 2012; 4(3):215-20. DOI: 10.1038/nchem.1242. View

13.

Wang W, Shi X, Wang S, Van Hove M, Lin N . Single-molecule resolution of an organometallic intermediate in a surface-supported Ullmann coupling reaction. J Am Chem Soc. 2011; 133(34):13264-7. DOI: 10.1021/ja204956b. View

14.

Zhang H, Chi L . Gold-Organic Hybrids: On-Surface Synthesis and Perspectives. Adv Mater. 2016; 28(47):10492-10498. DOI: 10.1002/adma.201602131. View

15.

Zhang R, Lyu G, Li D, Liu P, Lin N . Template-controlled Sonogashira cross-coupling reactions on a Au(111) surface. Chem Commun (Camb). 2017; 53(10):1731-1734. DOI: 10.1039/c6cc10091k. View

16.

Lin N, Stepanow S, Ruben M, Barth J . Surface-confined supramolecular coordination chemistry. Top Curr Chem. 2013; 287:1-44. DOI: 10.1007/128_2008_150. View

17.

Wiengarten A, Seufert K, Auwarter W, Ecija D, Diller K, Allegretti F . Surface-assisted dehydrogenative homocoupling of porphine molecules. J Am Chem Soc. 2014; 136(26):9346-54. DOI: 10.1021/ja501680n. View

18.

Ruffieux P, Wang S, Yang B, Sanchez-Sanchez C, Liu J, Dienel T . On-surface synthesis of graphene nanoribbons with zigzag edge topology. Nature. 2016; 531(7595):489-92. DOI: 10.1038/nature17151. View

19.

Kawai S, Saito S, Osumi S, Yamaguchi S, Foster A, Spijker P . Atomically controlled substitutional boron-doping of graphene nanoribbons. Nat Commun. 2015; 6:8098. PMC: 4560828. DOI: 10.1038/ncomms9098. View

20.

Moreno C, Vilas-Varela M, Kretz B, Garcia-Lekue A, Costache M, Paradinas M . Bottom-up synthesis of multifunctional nanoporous graphene. Science. 2018; 360(6385):199-203. DOI: 10.1126/science.aar2009. View