TY - JOUR
T1 - High-Yield Formation of Graphdiyne Macrocycles through On-Surface Assembling and Coupling Reaction
AU - Liu, Mengxi
AU - Li, Shichao
AU - Zhou, Jingyuan
AU - Zha, Zeqi
AU - Pan, Jinliang
AU - Li, Xin
AU - Zhang, Jin
AU - Liu, Zhongfan
AU - Li, Yuanchang
AU - Qiu, Xiaohui
N1 - Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/12/26
Y1 - 2018/12/26
N2 - Rationally designed halogenated hydrocarbons are widely used building blocks to fabricate covalent-bonded carbon nanostructures on surfaces through a reaction pathway involving generation and dissociation of organometallic intermediates and irreversible covalent bond formation. Here, we provide a comprehensive picture of the on-surface-assisted homocoupling reaction of 1,3-bis(2-bromoethynyl)benzene on Au(111), aiming for the synthesis of graphdiyne nanostructures. Submolecular resolution scanning tunneling microscopy and noncontact atomic force microscopy observations identify the organometallic intermediates and their self-assemblies formed in the dehalogenation process. The demetallization of the organometallic intermediates at increased temperatures produces butadiyne moieties that spontaneously formed two different covalent structures (i.e., graphdiyne zigzag chains and macrocycles), whose ratio was found to depend on the initial coverage of organometallic intermediates. At the optimal condition, the stepwise demetallization and cyclization led to a high-yield production of graphdiyne macrocycles up to 95%. Statistical analysis and theoretical calculations suggested that the favored formation of macrocycles resulted from the complex interplay between thermodynamic and kinetic processes involving the organometallic bonded intermediates and the covalently bonded butadiyne moieties.
AB - Rationally designed halogenated hydrocarbons are widely used building blocks to fabricate covalent-bonded carbon nanostructures on surfaces through a reaction pathway involving generation and dissociation of organometallic intermediates and irreversible covalent bond formation. Here, we provide a comprehensive picture of the on-surface-assisted homocoupling reaction of 1,3-bis(2-bromoethynyl)benzene on Au(111), aiming for the synthesis of graphdiyne nanostructures. Submolecular resolution scanning tunneling microscopy and noncontact atomic force microscopy observations identify the organometallic intermediates and their self-assemblies formed in the dehalogenation process. The demetallization of the organometallic intermediates at increased temperatures produces butadiyne moieties that spontaneously formed two different covalent structures (i.e., graphdiyne zigzag chains and macrocycles), whose ratio was found to depend on the initial coverage of organometallic intermediates. At the optimal condition, the stepwise demetallization and cyclization led to a high-yield production of graphdiyne macrocycles up to 95%. Statistical analysis and theoretical calculations suggested that the favored formation of macrocycles resulted from the complex interplay between thermodynamic and kinetic processes involving the organometallic bonded intermediates and the covalently bonded butadiyne moieties.
KW - graphdiyne macrocycle
KW - noncontact atomic force microscopy
KW - on-surface reaction
KW - organometallic intermediate
KW - scanning tunneling microscopy
KW - thermodynamic and kinetic control
UR - http://www.scopus.com/inward/record.url?scp=85058511124&partnerID=8YFLogxK
U2 - 10.1021/acsnano.8b07349
DO - 10.1021/acsnano.8b07349
M3 - Article
C2 - 30513200
AN - SCOPUS:85058511124
SN - 1936-0851
VL - 12
SP - 12612
EP - 12618
JO - ACS Nano
JF - ACS Nano
IS - 12
ER -