The linkage structures between monomers make great influence on the properties of polymers.The synthesis of some special linkage structures can be challenging,which is often overcome by employing special reaction cond...The linkage structures between monomers make great influence on the properties of polymers.The synthesis of some special linkage structures can be challenging,which is often overcome by employing special reaction conditions.Here,we build dihydropentalene linkage in poly-naphthalocyanine on Ag(110)surface.Scanning tunneling microscopy(STM)and non-contact atomic force microscopy(nc-AFM)measurements confirm the dihydropentalene linkage structure and a possible formation path with reconstruction steps is proposed.The controlled experiment on Ag(100)surface shows no dihydropentalene structures formed,which indicates the grooved substrate is necessary for the reconstruction.This work provides insights into the surface restricted reactions that can yield special structures in organic polymers.展开更多
Cyclic-conjugated linkages between planar-macrocydic molecules contribute to the robustness of the two-dimensional (2D) polymerization and extension of π-interactions. The fabrication of such linkages in 2D polymers ...Cyclic-conjugated linkages between planar-macrocydic 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 [\(1\overline 1 0\)] 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 [\(1\overline 1 0\)] 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.展开更多
基金the National Natural Science Foundation of China(Grant No.61888102)the National Key Research and Development Program of China(Grant Nos.2018YFA0305800 and 2019YFA0308500)+1 种基金Chinese Academy of Sciences(Grant Nos.XDB30000000,YSBR003,and 112111KYSB20160061)the Fundamental Research Funds for the Central Universities,China.
文摘The linkage structures between monomers make great influence on the properties of polymers.The synthesis of some special linkage structures can be challenging,which is often overcome by employing special reaction conditions.Here,we build dihydropentalene linkage in poly-naphthalocyanine on Ag(110)surface.Scanning tunneling microscopy(STM)and non-contact atomic force microscopy(nc-AFM)measurements confirm the dihydropentalene linkage structure and a possible formation path with reconstruction steps is proposed.The controlled experiment on Ag(100)surface shows no dihydropentalene structures formed,which indicates the grooved substrate is necessary for the reconstruction.This work provides insights into the surface restricted reactions that can yield special structures in organic polymers.
基金This work was financially supported by the National Key Research and Development Program of China(No.2016YFA0202300)the National Natural Science Foundation of China(Nos.61888102 and 61725107)+2 种基金Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB30000000)the International Partnership Program of Chinese Academy of Sciences(No.112111KYSB20160061)China Postdoctoral Science Foundation(No.2018M641511).
文摘Cyclic-conjugated linkages between planar-macrocydic 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 [\(1\overline 1 0\)] 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 [\(1\overline 1 0\)] 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.
