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Research Article

Construction of poly-naphthalocyanine linked by [4]-radialene-like structures on silver surfaces

Rongting Wu1,§,†, De-Liang Bao1,§, Linghao Yan1, Junhai Ren1, Yanfang Zhang1, Qi Zheng1, Ye-Liang Wang1, Qing Huan1( ), Shixuan Du1,2,3( ), Hong-Jun Gao1,2
Institute of Physics & University of Chinese Academy of Sciences, Chinese Academy of SciencesBeijing100190China
CAS Center for Excellence in Topological Quantum Computation, Chinese Academy of SciencesBeijing100190China
Songshan Lake Materials LaboratoryDongguan523808China

§ Rongting Wu and De-Liang Bao contributed equally to this work.

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Graphical Abstract

Abstract

Cyclic-conjugated linkages between planar-macrocyclic molecules contribute to the robustness of the two-dimensional (2D) polymerization and extension of π-interactions. The fabrication of such linkages in 2D polymers remains challenging. Combining scanning tunneling microscope (STM) measurements and density functional theory (DFT) calculations, we demonstrate a linear polymerization of metal-free naphthalocyanine (NPc) molecules with [4]-radialene-like linkages on silver surfaces. Experimentally, by depositing NPc molecules on the Ag(110) surface and subsequent annealing up to 750 K, one-dimensional polymers are constructed along the [11(_)0] direction. High-resolution STM images show a stem-leaf-like feature. STM simulations based on a linear polymer of NPc molecules linked by four-membered carbon rings, [4]-radialene-like structure, agree well with the experimental observations. DFT calculations reveal that the polymerization process includes detaching two-terminal H atoms of NPc molecules along [11(_)0] direction, then bonding with a neighboring dehydrogenated NPc molecule by forming a four-membered ring. The dehydrogenation process can be promoted by on-surface impurities such as additional H atoms. Similar polymerizations have been achieved on Ag(111) surfaces in an amorphous way. Moreover, the energy gap of the NPc molecule decreases after linear polymerization, suggesting a red-shift for its optical absorption/scattering spectrum. Our study offers a new route to polymerize conjugated molecules with extended planar π-interactions.

Keywords

polymerizationnaphthalocyanineπ-interaction extensionscanning tunneling microscopedensity functional theory calculation

References

1

Colson, J. W. ; Dichtel, W. R. Rationally synthesized two-dimensional polymers. Nat. Chem. 2013, 5, 453-465.
Crossref Google Scholar
2

Payamyar, P. ; King, B. T. ; Öttinger, H. C. ; Schlüter, A. D. Two-dimensional polymers: Concepts and perspectives. Chem. Commun. 2016, 52, 18-34.
Crossref Google Scholar
3

Grill, L. ; Hecht, S. Covalent on-surface polymerization. Nat. Chem. 2020, 12, 115-130.
Crossref Google Scholar
4

Schlüter, A. D. Mastering polymer chemistry in two dimensions. Commun. Chem. 2020, 3, 12.
Crossref Google Scholar
5

Cai, J. M. ; Ruffieux, P. ; Jaafar, R. ; Bieri, M. ; Braun, T. ; Blankenburg, S. ; Muoth, M. ; Seitsonen, A. P. ; Saleh, M. ; Feng, X. L. et al. Atomically precise bottom-up fabrication of graphene nanoribbons. Nature 2010, 466, 470-473.
Crossref Google Scholar
6

Ruffieux, P. ; Wang, S. Y. ; Yang, B. ; Sánchez-Sánchez, C. ; Liu, J. ; Dienel, T. ; Talirz, L. ; Shinde, P. ; Pignedoli, C. A. ; Passerone, D. et al. On-surface synthesis of graphene nanoribbons with zigzag edge topology. Nature 2016, 531, 489-492.
Crossref Google Scholar
7

Grill, L. ; Dyer, M. ; Lafferentz, L. ; Persson, M. ; Peters, M. V. ; Hecht, S. Nano-architectures by covalent assembly of molecular building blocks. Nat. Nanotechnol. 2007, 2, 687-691.
Crossref Google Scholar
8

Sánchez-Sánchez, C. ; Dienel, T. ; Deniz, O. ; Ruffieux, P. ; Berger, R. ; Feng, X. L. ; Müllen, K. ; Fasel, R. Purely armchair or partially chiral: Noncontact atomic force microscopy characterization of dibromo-bianthryl-based graphene nanoribbons grown on Cu(111). ACS Nano 2016, 10, 8006-8011.
Crossref Google Scholar
9

Zhong, D. Y. ; Franke, J. H. ; Podiyanachari, S. K. ; Blömker, T. ; Zhang, H. M. ; Kehr, G. ; Erker, G. ; Fuchs, H. ; Chi, L. F. Linear alkane polymerization on a gold surface. Science 2011, 334, 213-216.
Crossref Google Scholar
10

Gobbi, M. ; Orgiu, E. ; Samorí, P. When 2D materials meet molecules: Opportunities and challenges of hybrid organic/inorganic Van der Waals heterostructures. Adv. Mater. 2018, 30, 1706103.
Crossref Google Scholar
11

Jariwala, D. ; Marks, T. J. ; Hersam, M. C. Mixed-dimensional Van der Waals heterostructures. Nat. Mater. 2017, 16, 170-181.
Crossref Google Scholar
12

He, D. W. ; Zhang, Y. H. ; Wu, Q. S. ; Xu, R. ; Nan, H. Y. ; Liu, J. F. ; Yao, J. J. ; Wang, Z. L. ; Yuan, S. J. ; Li, Y. et al. Two-dimensional quasi-freestanding molecular crystals for high-performance organic field-effect transistors. Nat. Commun. 2014, 5, 5162.
Crossref Google Scholar
13

Yun, H. J. ; Choi, H. H. ; Kwon, S. K. ; Kim, Y. H. ; Cho, K. Polarity engineering of conjugated polymers by variation of chemical linkages connecting conjugated backbones. ACS Appl. Mater. Interfaces 2015, 7, 5898-5906.
Crossref Google Scholar
14

Liu, W. ; Luo, X. ; Bao, Y. ; Liu, Y. P. ; Ning, G. H. ; Abdelwahab, I. ; Li, L. J. ; Nai, C. T. ; Hu, Z. G. ; Zhao, D. et al. A two-dimensional conjugated aromatic polymer via C-C coupling reaction. Nat. Chem. 2017, 9, 563-570.
Crossref Google Scholar
15

Vasseur, G. ; Abadia, M. ; Miccio, L. A. ; Brede, J. ; Garcia-Lekue, A. ; de Oteyza, D. G. ; Rogero, C. ; Lobo-Checa, J. ; Ortega, J. E. Π band dispersion along conjugated organic nanowires synthesized on a metal oxide semiconductor. J. Am. Chem. Soc. 2016, 138, 5685-5692.
Crossref Google Scholar
16

Bi, S. ; Yang, C. ; Zhang, W. B. ; Xu, J. S. ; Liu, L. M. ; Wu, D. Q. ; Wang, X. C. ; Han, Y. ; Liang, Q. F. ; Zhang, F. Two-dimensional semiconducting covalent organic frameworks via condensation at arylmethyl carbon atoms. Nat. Commun. 2019, 10, 2467.
Crossref Google Scholar
17

Wang, W. H. ; Shi, X. Q. ; Wang, S. Y. ; Van Hove, M. A. ; Lin, N. Single-molecule resolution of an organometallic intermediate in a surface-supported ullmann coupling reaction. J. Am. Chem. Soc. 2011, 133, 13264-13267.
Crossref Google Scholar
18

Ren, J. H. ; Bao, D. L. ; Dong, L. ; Gao, L. ; Wu, R. T. ; Yan, L. H. ; Wang, A. W. ; Yan, J. H. ; Wang, Y. L. ; Huan, Q. et al. Lattice-directed construction of metal-organic molecular wires of pentacene on the Au(110) surface. J. Phys. Chem. C 2017, 121, 21650-21657.
Crossref Google Scholar
19

Spitler, E. L. ; Dichtel, W. R. Lewis acid-catalysed formation of two-dimensional phthalocyanine covalent organic frameworks. Nat. Chem. 2010, 2, 672-677.
Crossref Google Scholar
20

Wan, S. ; Guo, J. ; Kim, J. ; Ihee, H. ; Jiang, D. L. A photoconductive covalent organic framework: Self-condensed arene cubes composed of eclipsed 2D polypyrene sheets for photocurrent generation. Angew. Chem. , Int. Ed. 2009, 48, 5439-5442.
Crossref Google Scholar
21

Yang, S. J. ; Chu, M. ; Miao, Q. Connecting two phenazines with a four-membered ring: The synthesis, properties and applications of cyclobuta[1, 2-b: 3, 4-b']diphenazines. J. Mater. Chem. C 2018, 6, 3651-3657.
Crossref Google Scholar
22

Sanchez-Sanchez, C. ; Nicolaï, A. ; Rossel, F. ; Cai, J. M. ; Liu, J. Z. ; Feng, X. L. ; Müllen, K. ; Ruffieux, P. ; Fasel, R. ; Meunier, V. On-surface cyclization of ortho-dihalotetracenes to four- and six-membered rings. J. Am. Chem. Soc. 2017, 139, 17617-17623.
Crossref Google Scholar
23

Cui, P. ; Zhang, Q. ; Zhu, H. B. ; Li, X. X. ; Wang, W. Y. ; Li, Q. X. ; Zeng, C. G. ; Zhang, Z. Y. Carbon tetragons as definitive spin switches in narrow zigzag graphene nanoribbons. Phys. Rev. Lett. 2016, 116, 026802.
Crossref Google Scholar
24

Zhong, Y. ; Cheng, B. R. ; Park, C. ; Ray, A. ; Brown, S. ; Mujid, F. ; Lee, J. U. ; Zhou, H. ; Suh, J. ; Lee, K. H. et al. Wafer-scale synthesis of monolayer two-dimensional porphyrin polymers for hybrid superlattices. Science 2019, 366, 1379-1384.
Crossref Google Scholar
25

Liljeroth, P. ; Repp, J. ; Meyer, G. Current-induced hydrogen tautomerization and conductance switching of naphthalocyanine molecules. Science 2007, 317, 1203-1206.
Crossref Google Scholar
26

Huan, Q. ; Jiang, Y. ; Zhang, Y. Y. ; Ham, U. ; Ho, W. Spatial imaging of individual vibronic states in the interior of single molecules. J. Chem. Phys. 2011, 135, 014705.
Crossref Google Scholar
27

Yan, L. H. ; Wu, R. T. ; Bao, D. L. ; Ren, J. H. ; Zhang, Y. F. ; Zhang, H. G. ; Huang, L. ; Wang, Y. L. ; Du, S. X. ; Huan, Q. et al. Adsorption behavior of Fe atoms on a naphthalocyanine monolayer on Ag(111) surface. Chin. Phys. B 2015, 24, 076802.
Crossref Google Scholar
28

Kobayashi, N. ; Nakajima, S. I. ; Ogata, H. ; Fukuda, T. Synthesis, spectroscopy, and electrochemistry of tetra-tert-butylated tetraazaporphyrins, phthalocyanines, naphthalocyanines, and anthracocyanines, together with molecular orbital calculations. Chem. —Eur. J. 2004, 10, 6294-6312.
Crossref Google Scholar
29

Lim, B. ; Margulis, G. Y. ; Yum, J. H. ; Unger, E. L. ; Hardin, B. E. ; Grätzel, M. ; McGehee, M. D. ; Sellinger, A. Silicon-naphthalo/ phthalocyanine-hybrid sensitizer for efficient red response in dye-sensitized solar cells. Org. Lett. 2013, 15, 784-787.
Crossref Google Scholar
30

Pandey, R. ; Kerner, R. A. ; Menke, S. M. ; Holst, J. ; Josyula, K. V. B. ; Holmes, R. J. Tin naphthalocyanine complexes for infrared absorption in organic photovoltaic cells. Org. Electron. 2013, 14, 804-808.
Crossref Google Scholar
31

Bao, D. L. ; Zhang, Y. Y. ; Du, S. X. ; Pantelides, S. T. ; Gao, H. J. Barrierless on-surface metal incorporation in phthalocyanine-based molecules. J. Phys. Chem. C 2018, 122, 6678-6683.
Crossref Google Scholar
32

Sun, Q. ; Zhang, C. ; Cai, L. L. ; Xie, L. ; Tan, Q. G. ; Xu, W. On-surface formation of two-dimensional polymer via direct C-H activation of metal phthalocyanine. Chem. Commun. 2015, 51, 2836-2839.
Crossref Google Scholar
33

Lafferentz, L. ; Eberhardt, V. ; Dri, C. ; Africh, C. ; Comelli, G. ; Esch, F. ; Hecht, S. ; Grill, L. Controlling on-surface polymerization by hierarchical and substrate-directed growth. Nat. Chem. 2012, 4, 215-220.
Crossref Google Scholar
34

Lin, T. ; Shang, X. S. ; Adisoejoso, J. ; Liu, P. N. ; Lin, N. Steering on-surface polymerization with metal-directed template. J. Am. Chem. Soc. 2013, 135, 3576-3582.
Crossref Google Scholar
35

Kuang, G. W. ; Chen, S. Z. ; Wang, W. H. ; Lin, T. ; Chen, K. Q. ; Shang, X. S. ; Liu, P. N. ; Lin, N. Resonant charge transport in conjugated molecular wires beyond 10 nm range. J. Am. Chem. Soc. 2016, 138, 11140-11143.
Crossref Google Scholar
36

Abel, M. ; Clair, S. ; Ourdjini, O. ; Mossoyan, M. ; Porte, L. Single layer of polymeric Fe-phthalocyanine: An organometallic sheet on metal and thin insulating film. J. Am. Chem. Soc. 2011, 133, 1203-1205.
Crossref Google Scholar
37

Zhou, J. ; Sun, Q. Magnetism of phthalocyanine-based organometallic single porous sheet. J. Am. Chem. Soc. 2011, 133, 15113-15119.
Crossref Google Scholar
38

Wang, Y. ; Yuan, H. ; Li, Y. F. ; Chen, Z. F. Two-dimensional iron-phthalocyanine (Fe-Pc) monolayer as a promising single-atom-catalyst for oxygen reduction reaction: A computational study. Nanoscale 2015, 7, 11633-11641.
Crossref Google Scholar
39

Stipe, B. C. ; Rezaei, M. A. ; Ho, W. A variable-temperature scanning tunneling microscope capable of single-molecule vibrational spectroscopy. Rev. Sci. Instrum. 1999, 70, 137-143.
Crossref Google Scholar
40

Wu, R. T. ; Ren, J. H. ; Dong, L. ; Wang, Y. L. ; Huan, Q. ; Gao, H. J. Quasi-free-standing graphene nano-islands on ag(110), grown from solid carbon source. Appl. Phys. Lett. 2017, 110, 213107.
Crossref Google Scholar
41

Vanderbilt, D. Soft self-consistent pseudopotentials in a generalized eigenvalue formalism. Phys. Rev. B 1990, 41, 7892-7895.
Crossref Google Scholar
42

Kresse, G. ; Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 1996, 54, 11169-11186.
Crossref Google Scholar
43

Kresse, G. ; Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 1999, 59, 1758-1775.
Crossref Google Scholar
44

Perdew, J. P. ; Burke, K. ; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865-3868.
Crossref Google Scholar
45

Perdew, J. P. ; Chevary, J. A. ; Vosko, S. H. ; Jackson, K. A. ; Pederson, M. R. ; Singh, D. J. ; Fiolhais, C. Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation. Phys. Rev. B 1992, 46, 6671-6687.
Crossref Google Scholar
46

Krukau, A. V. ; Vydrov, O. A. ; Izmaylov, A. F. ; Scuseria, G. E. Influence of the exchange screening parameter on the performance of screened hybrid functionals. J. Chem. Phys. 2006, 125, 224106.
Crossref Google Scholar
47

Henkelman, G. ; Uberuaga, B. P. ; Jónsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 2000, 113, 9901-9904.
Crossref Google Scholar
48

Wu, X. ; Vargas, M. C. ; Nayak, S. ; Lotrich, V. ; Scoles, G. Towards extending the applicability of density functional theory to weakly bound systems. J. Chem. Phys. 2001, 115, 8748-8757.
Crossref Google Scholar
49

Wu, R. T. ; Yan, L. H. ; Zhang, Y. F. ; Ren, J. H. ; Bao, D. L. ; Zhang, H. G. ; Wang, Y. L. ; Du, S. X. ; Huan, Q. ; Gao, H. J. Self-assembled patterns and young's modulus of single-layer naphthalocyanine molecules on Ag(111). J. Phys. Chem. C 2015, 119, 8208-8212.
Crossref Google Scholar
50

Wu, R. T. ; Yan, L. H. ; Bao, D. L. ; Ren, J. H. ; Du, S. X. ; Wang, Y. L. ; Huan, Q. ; Gao, H. J. Self-assembly evolution of metal-free naphthalocyanine molecules on Ag(111) at the submonolayer coverage. J. Phys. Chem. C 2019, 123, 7202-7208.
Crossref Google Scholar
51

Wu, R. T. ; Bao, D. L. ; Yan, L. H. ; Wang, Y. L. ; Ren, J. H. ; Zhang, Y. F. ; Huan, Q. ; Zhang, Y. Y. ; Du, S. X. ; Pantelides, S. T. ; Gao, H. J. Direct visualization of hydrogen-transfer intermediate states by scanning tunneling microscopy. J. Phys. Chem. Lett. 2020, 11, 1536-1541.
Crossref Google Scholar
52

Pham, T. A. ; Song, F. ; Stöhr, M. Supramolecular self-assembly of metal-free naphthalocyanine on Au(111). Phys. Chem. Chem. Phys. 2014, 16, 8881-8885.
Crossref Google Scholar
53

Du, S. X. ; Gao, H. J. ; Seidel, C. ; Tsetseris, L. ; Ji, W. ; Kopf, H. ; Chi, L. F. ; Fuchs, H. ; Pennycook, S. J. ; Pantelides, S. T. Selective nontemplated adsorption of organic molecules on nanofacets and the role of bonding patterns. Phys. Rev. Lett. 2006, 97, 156105.
Crossref Google Scholar
54

Sun, X. P. ; Hyeon Ko, S. ; Zhang, C. ; Ribbe, A. E. ; Mao, C. D. Surface-mediated DNA self-assembly. J. Am. Chem. Soc. 2009, 131, 13248-13249.
Crossref Google Scholar
55

Sun, Q. ; Zhang, C. ; Kong, H. H. ; Tan, Q. G. ; Xu, W. On-surface aryl-aryl coupling via selective C-H activation. Chem. Commun. 2014, 50, 11825-11828.
Crossref Google Scholar
56

Refaely-Abramson, S. ; Sharifzadeh, S. ; Jain, M. ; Baer, R. ; Neaton, J. B. ; Kronik, L. Gap renormalization of molecular crystals from density-functional theory. Phys. Rev. B 2013, 88, 081204.
Crossref Google Scholar
57

El-Khouly, M. E. ; El-Mohsnawy, E. ; Fukuzumi, S. Solar energy conversion: From natural to artificial photosynthesis. J. Photochem. Photobiol. C 2017, 31, 36-83.
Crossref Google Scholar
58

Polman, A. ; Knight, M. ; Garnett, E. C. ; Ehrler, B. ; Sinke, W. C. Photovoltaic materials: Present efficiencies and future challenges. Science 2016, 352, aad4424.
Crossref Google Scholar
Nano Research
Volume 14 Issue 12,
December 2021
Pages 4563-4568
DOI: 10.1007/s12274-021-3374-3
Cite this article:
Wu R, Bao D-L, Yan L, et al. Construction of poly-naphthalocyanine linked by [4]-radialene-like structures on silver surfaces. Nano Research, 2021, 14(12): 4563-4568. https://doi.org/10.1007/s12274-021-3374-3
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Received: 01 December 2020
Revised: 21 January 2021
Accepted: 31 January 2021
Published: 03 March 2021
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021
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