Citation: Shaoze WANG, Aimei ZHOU, Yunhui WANG, Lei SUN. Diversified on-surface self-assembly of Cu₃(HOTP)₂ fragments: Atomic characterization of oxidation and deprotonation effects[J]. Chinese Journal of Inorganic Chemistry, ;2026, 42(11): 2411-2419. doi: 10.11862/CJIC.20260211 shu

Diversified on-surface self-assembly of Cu₃(HOTP)₂ fragments: Atomic characterization of oxidation and deprotonation effects

Shaoze WANG ^{1, 2, 3} ,
Aimei ZHOU ^{1, 3} ,
Yunhui WANG ⁴ ,
Lei SUN ^{1, 2, 3,,}

1.
Department of Chemistry, School of Science and Research Center for Industries of the Future, Westlake University, Hangzhou 310030, China
2.
Department of Physics, School of Science and Research Center for Industries of the Future, Westlake University, Hangzhou 310030, China
3.
Institute of Natural Sciences, Westlake Institute for Advanced Study, Hangzhou 310024, China
4.
Instrumentation and Service Center for Physical Sciences, Westlake University, Hangzhou 310030, China

Corresponding author: Lei SUN, sunlei@westlake.edu.cn
Received Date: 2 July 2026
Revised Date: 22 September 2026

Figures(5)

Under ultra-high vacuum, surface synthesis of 2D conjugated metal-organic frameworks (MOFs) was carried out through molecular beam epitaxy (MBE) growth to address the challenge of traditional solvothermal methods in achieving large-scale, defect-free single-crystal synthesis. Here, we chose an iconic 2D conjugated MOF, Cu₃(HOTP)₂ (HOTP represents the deprotonated derivative of 2,3,6,7,10,11-hexahydroxytriphenylene), as a case study to investigate the diversified self-assembly of Cu atoms and HHTP ligands, as well as the synthesis mechanism of the MOF fragment on the surface with and without O₂ annealing conditions by scanning tunneling microscopy. The results show that dumbbell-shaped [Cu(HOTP)₂] complexes, the target fragment of MOFs, can be successfully generated in an O₂ atmosphere, yet large-area extended MOFs remain elusive, highlighting oxidation and ligand deprotonation as two key factors that hinder the on-surface synthesis of Cu₃(HOTP)₂.
- metal-organic frameworks,
- Cu₃(HOTP)₂,
- scanning tunneling microscopy,
- molecular beam epitaxy growth,
- self-assembly
1. [1]
  PASCANU V, GONZÁLEZ MIERA G, INGE A K, MARTÍN-MATUTE B. Metal-organic frameworks as catalysts for organic synthesis: A critical perspective[J]. J. Am. Chem. Soc., 2019, 141(18): 7223-7234 doi: 10.1021/jacs.9b00733
2. [2]
  KRENO L E, LEONG K, FARHA O K, ALLENDORF M, VAN DUYNE R P, HUPP J T. Metal-organic framework materials as chemical sensors[J]. Chem. Rev., 2012, 112: 1105-1125 doi: 10.1021/cr200324t
3. [3]
  YAMABAYASHI T, ATZORI M, TESI L, COSQUER G, SANTANNI F, BOULON M E, MORRA E, BENCI S, TORRE R, CHIESA M, SORACE L, SESSOLI R, YAMASHITA M. Scaling up electronic spin qubits into a three-dimensional metal-organic framework[J]. J. Am. Chem. Soc., 2018, 140(38): 12090-12101 doi: 10.1021/jacs.8b06733
4. [4]
  MALLAKPOUR S, NIKKHOO E, HUSSAIN C M. Application of MOF materials as drug delivery systems for cancer therapy and dermal treatment[J]. Coord. Chem. Rev., 2022, 451: 214262 doi: 10.1016/j.ccr.2021.214262
5. [5]
  HUANG X, SHENG P, TU Z Y, ZHANG F J, WANG J H, GENG H, ZOU Y, DI C A, YI Y P, SUN Y M, XU W, ZHU D B. A two-dimensional π-d conjugated coordination polymer with extremely high electrical conductivity and ambipolar transport behavior[J]. Nat. Commun., 2015, 6: 7408 doi: 10.1038/ncomms8408
6. [6]
  HUANG X, ZHANG S, LIU L Y, YU L, CHEN G F, XU W, ZHU D B. Superconductivity in a copper(Ⅱ)-based coordination polymer with perfect kagome structure[J]. Angew. Chem.—Int. Edit., 2018, 57(1): 146-150 doi: 10.1002/anie.201707568
7. [7]
  PAN Z C, HUANG X, FAN Y L, WANG S Z, LIU Y Y, CONG X Z, ZHANG T S, QI S C, XING Y, ZHENG Y Q, LI J, ZHANG X M, XU W, SUN L, WANG J, DOU J H. Synthesis and structure of a non-van-der-Waals two-dimensional coordination polymer with superconductivity[J]. Nat. Commun., 2024, 15: 9342 doi: 10.1038/s41467-024-53786-1
8. [8]
  MISUMI Y, YAMAGUCHI A, ZHANG Z Y, MATSUSHITA T, WADA N, TSUCHIIZU M, AWAGA K. Quantum spin liquid state in a two-dimensional semiconductive metal-organic framework[J]. J. Am. Chem. Soc., 2020, 142(39): 16513-16517 doi: 10.1021/jacs.0c05472
9. [9]
  JIANG W, NI X J, LIU F. Exotic topological bands and quantum states in metal-organic and covalent-organic frameworks[J]. Acc. Chem. Res., 2021, 54(2): 416-426 doi: 10.1021/acs.accounts.0c00652
10. [10]
  WU M H, WANG Z J, LIU J W, LI W B, FU H H, SUN L, LIU X, PAN M H, WENG H M, DINCĂ M. Conetronics in 2D metal-organic frameworks: Double/half Dirac cones and quantum anomalous Hall effect[J]. 2D Mater., 2017, 4(1): 015015 doi: 10.1088/2053-1583/4/1/015015
11. [11]
  GU F B, SHU S S, PATRICK C E, CASTELL M R. Scanning tunneling microscopy of bimetallic Ni/Co-HITP metal-organic framework monolayers[J]. J. Phys. Chem. C, 2024, 128(41): 17797-17805 doi: 10.1021/acs.jpcc.4c06050
12. [12]
  GAO Z A, GAO Y F, HUA M Q, LIU J, HUANG L, LIN N. Design and synthesis of a single-layer ferromagnetic metal-organic framework with topological nontrivial gaps[J]. J. Phys. Chem. C, 2020, 124(49): 27017-27023 doi: 10.1021/acs.jpcc.0c08140
13. [13]
  GAO Z A, HSU C H, LIU J, CHUANG F C, ZHANG R, XIA B W, XU H, HUANG L, JIN Q, LIU P N, LIN N. Synthesis and characterization of a single-layer conjugated metal-organic structure featuring a non-trivial topological gap[J]. Nanoscale, 2019, 11(3): 878-881 doi: 10.1039/C8NR08477G
14. [14]
  LOWE B, FIELD B, HELLERSTEDT J, CEDDIA J, NOURSE H L, POWELL B J, MEDHEKAR N V, SCHIFFRIN A. Local gate control of Mott metal-insulator transition in a 2D metal-organic framework[J]. Nat. Commun., 2024, 15: 3559 doi: 10.1038/s41467-024-47766-8
15. [15]
  KUMAR D, HELLERSTEDT J, FIELD B, LOWE B, YIN Y F, MEDHEKAR N V, SCHIFFRIN A. Manifestation of strongly correlated electrons in a 2D Kagome metal-organic framework[J]. Adv. Funct. Mater., 2021, 31(48): 2106474 doi: 10.1002/adfm.202106474
16. [16]
  DAY R W, BEDIAKO D K, REZAEE M, PARENT L R, SKORUPSKII G, ARGUILLA M Q, HENDON C H, STASSEN I, GIANNESCHI N C, KIM P, DINCĂ M. Single crystals of electrically conductive two-dimensional metal-organic frameworks: Structural and electrical transport properties[J]. ACS Cent. Sci., 2019, 5(12): 1959-1964 doi: 10.1021/acscentsci.9b01006
17. [17]
  FAN Y L, GUO J K, YAO Z F, ZHANG Z H, ZHANG H Y, HUANG X, PAN Z C, YANG L M, MA C, WU X Y, LE K N, CHEN T Y, XU Z C, ZHANG L, CHEN H, ZHAO T Y, QIAO S, ZHANG T S, JI Q Q, ZHENG Y Q, SUN L, SKORUPSKII G, ARGUILLA M Q, YI Y P, HENDON C H, DINCĂ M, LI J, DOU J H. Programming stacking order in conducting van der Waals metal-organic frameworks through ligand aggregation[J]. Nat. Chem., 2026, 18: 1543-1552 doi: 10.1038/s41557-026-02180-z
18. [18]
  CHEN H, ZHAO T Y, LI W S, HE L, GUO J K, YAO Z F, MA C, FAN Y L, JIANG B, ZHANG L, ZHANG H Y, LIU S Z, ZHANG Z Y, SUN L, YANG L M, BROZEK C K, ZHENG Y Q, LI J, CHEN T Y, SUN J L, DOU J H. Aligning chemical kinetics with crystallization enables millimeter-scale single crystals of conductive MOFs[J]. J. Am. Chem. Soc., 2026, 148(26): 27710-27721 doi: 10.1021/jacs.6c07951
19. [19]
  DU X, ZHANG J N, WANG H L, HUANG Z H, GUO A K, ZHAO L, NIU Y, LI X L, WU B, LIU Y Q. Solid-solid interface growth of conductive metal-organic framework nanowire arrays and their supercapacitor application[J]. Mater. Chem. Front., 2020, 4(1): 243-251 doi: 10.1039/C9QM00527G
20. [20]
  YAO M S, LV X J, FU Z H, LI W H, DENG W H, WU G D, XU G. Layer-by-layer assembled conductive metal-organic framework nanofilms for room-temperature chemiresistive sensing[J]. Angew. Chem.—Int. Edit., 2017, 56(52): 16510-16514 doi: 10.1002/anie.201709558
21. [21]
  GAO S Y, HUANG Y, TAN J, XU J M, ZHAO L, ZHOU W, YANG Z H, SUN J, GONG H. Self-powered infrared photodetectors with ultra-high speed and detectivity based on amorphous Cu-based MOF films[J]. ACS Appl. Mater. Interfaces, 2023, 15(27): 32637-32646 doi: 10.1021/acsami.3c05121
22. [22]
  ROCHEFORT A, VERNISSE L, GÓMEZ-HERRERO A C, SÁNCHEZ-SÁNCHEZ C, MARTÍN-GAGO J A, CHÉRIOUX F, CLAIR S, CORAUX J, MARTÍNEZ J I. Role of the structure and reactivity of Cu and Ag surfaces in the formation of a 2D metal-hexahydroxytriphenylene network[J]. J. Phys. Chem. C, 2021, 125(31): 17333-17341 doi: 10.1021/acs.jpcc.1c03976
23. [23]
  GIOVANELLI L, OURDJINI O, ABEL M, PAWLAK R, FUJII J, PORTE L, THEMLIN J M, CLAIR S. Combined photoemission spectroscopy and scanning tunneling microscopy study of the sequential dehydrogenation of hexahydroxytriphenylene on Ag(111)[J]. J. Phys. Chem. C, 2014, 118(27): 14899-14904 doi: 10.1021/jp501849h
24. [24]
  CORATGER R, CALMETTES B, ABEL M, PORTE L. STM observations of the first polymerization steps between hexahydroxy-tri-phenylene and benzene-di-boronic acid molecules[J]. Surf. Sci., 2011, 605(7/8): 831-837
25. [25]
  LEE Y, JEONG C, BAEK S, KANG M J, CHANG M H, KIM Y H, KAHNG S J. Spin and stability of on-surface synthesized Ni-organic complexes on Au(111)[J]. Appl. Surf. Sci., 2026, 720: 165219 doi: 10.1016/j.apsusc.2025.165219
26. [26]
  YEAP G Y, RAHIM M A, LIN C M, LIN H C, MAETA N, ITO M M. Synthesis and liquid crystalline studies of disc-shaped molecule on azo-bridged benzothiazolephenyl ethers[J]. J. Mol. Liq., 2016, 223: 734-740 doi: 10.1016/j.molliq.2016.08.110
27. [27]
  WANG S, WANG A L, YANG C K, GAO R, LIU X, CHEN J, WANG Z N, ZENG Q H, LIU X F, ZHOU H H, ZHANG L Y. Six-arm star polymer based on discotic liquid crystal as high performance all-solid-state polymer electrolyte for lithium-ion batteries[J]. J. Power Sources, 2018, 395: 137-147 doi: 10.1016/j.jpowsour.2018.05.069
1. [1]
  Xiaofei NIU , Ke WANG , Fengyan SONG , Shuyan YU . Self-assembly of [Pd₆(L)₄]⁸⁺-type macrocyclic complexes for fluorescent sensing of HSO₃^-. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1233-1242. doi: 10.11862/CJIC.20240057
2. [2]
  Ruolin CHENG , Yue WANG , Fei YANG , Huagen LIANG , Shijian LU . Application of metal-organic frameworks (MOFs) in photocatalytic CO₂ cycloaddition reaction: A mini review. Chinese Journal of Inorganic Chemistry, 2025, 41(12): 2429-2440. doi: 10.11862/CJIC.20250242
3. [3]
  Yujing HUANG , Yuan GOU , Kexin JI , Xingcai HUANG , Siyuan CHEN , Jiaojiao KONG , Yanqing WANG . Thiazolo[5,4-d]thiazole fluorophore functionalization in 2D Cd(Ⅱ) metal-organic frameworks triggering a luminescence enhancement for highly sensitive aqueous antibiotic sensing. Chinese Journal of Inorganic Chemistry, 2026, 42(9): 1945-1958. doi: 10.11862/CJIC.20260147
4. [4]
  Wei GUO , Zhuoyi GUO , Xiaoxin LI , Wei ZHANG , Juanzhi YAN , Tingting GUO . Electrochemical sensor based on a Co(Ⅱ)-based metal-organic framework for the detection of Cd²⁺ and Pb²⁺. Chinese Journal of Inorganic Chemistry, 2025, 41(9): 1889-1902. doi: 10.11862/CJIC.20250097
5. [5]
  Xuetian WANG , Jijiang WANG , Long TANG , Erlin YUE , Xiao WANG , Yuqi ZHANG . A three-dimensional zinc(Ⅱ) metal-organic framework based on nitrogen-containing ligands for the detection of 2,4-dinitrophenylhydrazine and tetracycline. Chinese Journal of Inorganic Chemistry, 2026, 42(4): 861-871. doi: 10.11862/CJIC.20250294
6. [6]
  Jimin HOU , Mengyang LI , Chunhua GONG , Shaozhuang ZHANG , Caihong ZHAN , Hao XU , Jingli XIE . Synthesis, structures, and properties of metal-organic frameworks based on bipyridyl ligands and isophthalic acid. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 549-560. doi: 10.11862/CJIC.20240348
7. [7]
  Jiaxuan YANG , Chenfa DENG , Jingyang LIU , Chenzexi XU , Hongxin CHEN , Yahui ZHU , Ying LI , Shuhua WANG , Rongping ZHOU , Chao CHEN . Advances in selective hydrogenation of α, β-unsaturated aldehydes/ketones catalyzed by metal-organic frameworks and their derivatives: A review. Chinese Journal of Inorganic Chemistry, 2025, 41(10): 1973-2010. doi: 10.11862/CJIC.20250175
8. [8]
  Yutong Xiong , Ting Meng , Wendi Luo , Bin Tu , Shuai Wang , Qingdao Zeng . Molecular conformational effects on co-assembly systems of low-symmetric carboxylic acids investigated by scanning tunneling microscopy. Chinese Journal of Structural Chemistry, 2025, 44(2): 100511-100511. doi: 10.1016/j.cjsc.2025.100511
9. [9]
  Haifeng ZHENG , Xingzhe GUO , Yunwei WEI , Xinfang WANG , Huimin QI , Yuting YAN , Jie ZHANG , Bingwen LI . Post-synthetic modification strategy to construct Co-MOF composites for boosting oxygen evolution reaction activity. Chinese Journal of Inorganic Chemistry, 2026, 42(1): 193-202. doi: 10.11862/CJIC.20250029
10. [10]
  Xin ZHANG , Xinyi JIAO , Wanqiao BAI , Xuehua SUN , Huali CUI , Yixia REN , Hongmei CHAI . Flexible Gd-MOF@PMMA/BMA composite film fluorescent sensor for highly sensitive detection of tyramine in bananas. Chinese Journal of Inorganic Chemistry, 2026, 42(2): 217-226. doi: 10.11862/CJIC.20250219
11. [11]
  Xiaoyu CHEN , Fei DOU , Juan AN , Mingyuan PANG , Min YANG , Haohao ZHANG , Laixin HONG , Zhen KONG , Kongming HU , Yaqing HU , Huan PANG . MOF-based materials for fast charging batteries: Mechanistic insights, application advances, and future perspectives. Chinese Journal of Inorganic Chemistry, 2026, 42(9): 1816-1844. doi: 10.11862/CJIC.20250383
12. [12]
  Bin Yao , Yao Bu , Hongfei Sun , Guowang Li , Xianying Wu , Wei Wang . Interlocked covalent organic cages: Design, synthesis, and self-assembly. Chinese Chemical Letters, 2026, 37(1): 111894-. doi: 10.1016/j.cclet.2025.111894
13. [13]
  Ya-Jie Zhu , Zhi-Min Lv , Hao-Feng Zhu , Qi-Yan Qi , Shang-Bo Yu , Jia Tian , Wei Zhou , Zhan-Ting Li . Self-assembly of disassemblable supramolecular organic frameworks for doxorubicin delivery, photofrin posttreatment phototoxicity inhibition and heparin neutralization. Chinese Chemical Letters, 2026, 37(1): 111353-. doi: 10.1016/j.cclet.2025.111353
14. [14]
  Ying Zhao , Yao He , Jian-Xin Yang , Wen-Jie Liu , Dan Tian , Francisco Aznarez , Le-Le Gong , Li-Long Dang , Lu-Fang Ma . Controllable self-assembly and photothermal conversion of metalla[2]catenanes induced by synergistic effect of free radicals and stacking interactions. Chinese Chemical Letters, 2025, 36(12): 111460-. doi: 10.1016/j.cclet.2025.111460
15. [15]
  Jiayi Lu , Yizhang Li , Hao Jiang , Zhiwen Zhu , Fengru Zheng , Qiang Sun . Preparing sub-monolayer metals with continuous coverage spread for high-throughput growth of metal-organic frameworks. Chinese Chemical Letters, 2025, 36(3): 110394-. doi: 10.1016/j.cclet.2024.110394
16. [16]
  Youlin SI , Shuquan SUN , Junsong YANG , Zijun BIE , Yan CHEN , Li LUO . Synthesis and adsorption properties of Zn(Ⅱ) metal-organic framework based on 3, 3', 5, 5'-tetraimidazolyl biphenyl ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1755-1762. doi: 10.11862/CJIC.20240061
17. [17]
  Xufei Li , Junfa Fu , Weiqiu Huang , Zhaoqiang Zhang , Xiaofang Lv , Jiahao Kang , Jixing Xu , Jiahua Cheng , Yuhao Lu , Yitong Sun . Modification of open metal sites in metal-organic frameworks for the enhancement of CO2 capture and alkane separation. Chinese Journal of Structural Chemistry, 2026, 45(6): 100892-100892. doi: 10.1016/j.cjsc.2026.100892
18. [18]
  Bin XU , Shufeng ZHANG , Feifan LANG , Chunyan NI , Bing WU , Jianping LANG . Photoreactive pyrene-based Zn?? metal-organic frameworks: Solid-state [2+2] cycloaddition and tunable luminescence. Chinese Journal of Inorganic Chemistry, 2026, 42(10): 2119-2126. doi: 10.11862/CJIC.20260140
19. [19]
  Guoshuai ZHANG , Peirong QI , Yaqi LI , Shengyuan CHANG . Solvent-regulated self-assembly of cobalt-p-sulfosulfonylcalix[4]arene frameworks with thiophene-2,5-dicarboxylic acid. Chinese Journal of Inorganic Chemistry, 2026, 42(10): 2245-2258. doi: 10.11862/CJIC.20260042
20. [20]
  Changhui Yu , Peng Shang , Huihui Hu , Yuening Zhang , Xujin Qin , Linyu Han , Caihe Liu , Xiaohan Liu , Minghua Liu , Yuan Guo , Zhen Zhang . Evolution of template-assisted two-dimensional porphyrin chiral grating structure by directed self-assembly using chiral second harmonic generation microscopy. Chinese Chemical Letters, 2024, 35(10): 109805-. doi: 10.1016/j.cclet.2024.109805

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(97)
HTML views(8)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Diversified on-surface self-assembly of Cu3(HOTP)2 fragments: Atomic characterization of oxidation and deprotonation effects

Metrics

通讯作者: 陈斌, bchen63@163.com

Diversified on-surface self-assembly of Cu₃(HOTP)₂ fragments: Atomic characterization of oxidation and deprotonation effects