Five-Vertex Lanthanide Coordination on Surfaces: A Route to Sophisticated Nanoarchitectures and Tessellations

We report a combined scanning tunneling microscopy and density functional theory study on the formation of intricate networks involving a flexible 5-fold carbonitrile–lanthanide (cerium or gadolinium) coordination. By employing linear linkers equipped with terminal carbonitrile functional groups, and by tuning the local rare-earth to molecule stoichiometry, architectures evidencing high spatial complexity become manifested, including disordered islands of pentameric and nonameric supramolecules, a 2D hierarchical short-range orientational disordered network, and a 2D Archimedean snub square tessellation of the surface, which coexists with minority 2D Archimedean elongated triangular tiling motifs. The combination of both the intricate structural features and the unique properties of lanthanide elements prospects great potential in a variety of fields such as magnetism and catalysis. Furthermore, the expression of Archimedean tiling motifs based on 5-fold vertexes suggests a route to the design of self-ass...

[1]  Natalie A. Wasio,et al.  Self-assembly of hydrogen-bonded two-dimensional quasicrystals , 2014, Nature.

[2]  J. Barth,et al.  Controlled manipulation of gadolinium-coordinated supramolecules by low-temperature scanning tunneling microscopy. , 2014, Nano letters.

[3]  Wolf Widdra,et al.  Quasicrystalline structure formation in a classical crystalline thin-film system , 2013, Nature.

[4]  A. Seitsonen,et al.  Five-vertex Archimedean surface tessellation by lanthanide-directed molecular self-assembly , 2013, Proceedings of the National Academy of Sciences.

[5]  A. Seitsonen,et al.  Hexagonal boron nitride on transition metal surfaces , 2013, Theoretical Chemistry Accounts.

[6]  A. Seitsonen,et al.  Nature of the attractive interaction between proton acceptors and organic ring systems. , 2012, Physical chemistry chemical physics : PCCP.

[7]  J. Barth,et al.  Two-dimensional short-range disordered crystalline networks from flexible molecular modules. , 2012, ACS nano.

[8]  Lei Dong,et al.  Structural transformation of two-dimensional metal-organic coordination networks driven by intrinsic in-plane compression. , 2011, Journal of the American Chemical Society.

[9]  K. Kern,et al.  Surface-Confined Metal?Organic Nanostructures from Co-Directed Assembly of Linear Terphenyl-dicarbonitrile Linkers on Ag(111) , 2010 .

[10]  J. Barth,et al.  Self-assembly of flexible one-dimensional coordination polymers on metal surfaces. , 2010, Journal of the American Chemical Society.

[11]  S. Grimme,et al.  A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. , 2010, The Journal of chemical physics.

[12]  K. Kern,et al.  Rational design of two-dimensional nanoscale networks by electrostatic interactions at surfaces. , 2010, ACS nano.

[13]  J. Barth,et al.  Random two-dimensional string networks based on divergent coordination assembly. , 2010, Nature chemistry.

[14]  L. Bartels.  Tailoring molecular layers at metal surfaces. , 2010, Nature chemistry.

[15]  J. Barth,et al.  Surface-assisted assembly of discrete porphyrin-based cyclic supramolecules. , 2010, Nano letters.

[16]  M. Hove,et al.  Two-dimensional metal-organic coordination networks of Mn-7,7,8,8-tetracyanoquinodimethane assembled on Cu(100): Structural, electronic, and magnetic properties , 2009 .

[17]  Christopher B. Murray,et al.  Quasicrystalline order in self-assembled binary nanoparticle superlattices , 2009, Nature.

[18]  J. Barth.  Fresh perspectives for surface coordination chemistry , 2009 .

[19]  Yunqi Liu,et al.  Improvements in Stability and Performance of N,N′‐Dialkyl Perylene Diimide‐Based n‐Type Thin‐Film Transistors , 2009 .

[20]  K. Kern,et al.  Chiral kagomé lattice from simple ditopic molecular bricks. , 2008, Journal of the American Chemical Society.

[21]  Clemens Bechinger,et al.  Archimedean-like tiling on decagonal quasicrystalline surfaces , 2008, Nature.

[22]  A. Arnau,et al.  Metal-organic honeycomb nanomeshes with tunable cavity size. , 2007, Nano letters.

[23]  Joost VandeVondele,et al.  Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases. , 2007, The Journal of chemical physics.

[24]  T. Gemma,et al.  Photonic band structure calculations of two-dimensional Archimedean tiling patterns , 2007 .

[25]  Y. Matsushita,et al.  Polymeric quasicrystal: mesoscopic quasicrystalline tiling in ABC star polymers. , 2007, Physical review letters.

[26]  J. Barth,et al.  Molecular architectonic on metal surfaces. , 2007, Annual review of physical chemistry.

[27]  K. Kern,et al.  Engineering atomic and molecular nanostructures at surfaces , 2005, Nature.

[28]  Michele Parrinello,et al.  Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach , 2005, Comput. Phys. Commun..

[29]  Bin Chen,et al.  Liquid Crystalline Networks Composed of Pentagonal, Square, and Triangular Cylinders , 2005, Science.

[30]  K. Kern,et al.  Steering molecular organization and host–guest interactions using two-dimensional nanoporous coordination systems , 2004, Nature materials.

[31]  K. Kern,et al.  Modular assembly of two-dimensional metal-organic coordination networks at a metal surface. , 2003, Angewandte Chemie.

[32]  K. Kern,et al.  Real-time single-molecule imaging of the formation and dynamics of coordination compounds. , 2002, Angewandte Chemie.

[33]  Yingkai Zhang,et al.  Comment on “Generalized Gradient Approximation Made Simple” , 1998 .

[34]  Michele Parrinello,et al.  A hybrid Gaussian and plane wave density functional scheme , 1997 .

[35]  M. Teter,et al.  Separable dual-space Gaussian pseudopotentials. , 1995, Physical review. B, Condensed matter.

[36]  J. Barth,et al.  Surface-confined supramolecular coordination chemistry. , 2009, Topics in current chemistry.

[37]  J. Bünzli.  Benefiting from the unique properties of lanthanide ions. , 2006, Accounts of chemical research.