Templated ceramic microstructures by using the breath-figure method.

We describe the synthesis of two cyclobutadiene(cyclopentadienyl)cobalt-containing poly(p-phenylene ethynylene)s (PPEs) and their use as precursors for stable ceramic surface coatings. Organometallic PPEs were shaped into hexagonally ordered assemblies by using the breath-figure method. Such breath figures can be washed away with an appropriate solvent. Upon pyrolysis at 500 degrees C under either nitrogen or air, the bubble arrays persist as ceramics and are insoluble in organic solvents or water. The formed pyrolyzed bubble arrays were analyzed by optical and scanning electron microscopy, as well as energy dispersive X-ray microanalysis (EDX). The composition of the ceramic materials is discussed based on EDX and IR data.

[1]  C. Knobler,et al.  Growth of breath figures. , 1986, Physical review letters.

[2]  Mark D. Smith,et al.  A simple route to (tetraethynylcyclobutadiene)cyclopentadienylcobalt , 2002 .

[3]  G. Ozin,et al.  Polyferrocenylsilane and Magnetic Ceramic Microspheres , 2001 .

[4]  O. Velev,et al.  Microstructured Porous Silica Obtained via Colloidal Crystal Templates , 1998 .

[5]  Jin Zhai,et al.  Super-hydrophobic surfaces: From natural to artificial , 2002 .

[6]  James N. Wilson,et al.  Permanent bubble arrays from a cross-linked poly(para-phenyleneethynylene): picoliter holes without microfabrication. , 2004, Journal of the American Chemical Society.

[7]  U. Bunz,et al.  Poly(aryleneethynylene)s: Syntheses, Properties, Structures, and Applications. , 2000, Chemical reviews.

[8]  G. Ozin,et al.  Large-scale synthesis of a silicon photonic crystal with a complete three-dimensional bandgap near 1.5 micrometres , 2000, Nature.

[9]  F. GILLMAN,et al.  German East African Dinosaurs , 1911, Nature.

[10]  G. Ozin,et al.  Ordered 2D arrays of ferromagnetic Fe/Co nanoparticle rings from a highly metallized metallopolymer precursor , 2004 .

[11]  K. Vollhardt,et al.  Bicyclobutadienylene(tricyclo[4.2.0.02,5]octa-1,3,5,7-tetraene)-.eta.5-cyclopentadienylcobalt. A possible intermediate in the remarkable gas phase rearrangement of 1,2-diethynyl-.eta.4-cyclobutadiene-.eta.5-cyclopentadienylcobalt , 1978 .

[12]  U. Bunz,et al.  Facile Microstructuring of Organic Semiconducting Polymers by the Breath Figure Method: Hexagonally Ordered Bubble Arrays in Rigid Rod‐Polymers , 2004 .

[13]  Christopher B. Murray,et al.  Synthesis and Characterization of Monodisperse Nanocrystals and Close-Packed Nanocrystal Assemblies , 2000 .

[14]  E. Negishi,et al.  Palladium-catalyzed alkynylation. , 2003, Chemical reviews.

[15]  Raju,et al.  Shaped ceramics with tunable magnetic properties from metal-containing polymers , 2000, Science.

[16]  H. Yabu,et al.  Preparation of Honeycomb-Patterned Polyimide Films by Self-Organization , 2003 .

[17]  K. Vollhardt,et al.  Synthesis, Crystal Structure, and Explosive Decomposition of 1,2:5,6:11,12:15,16- Tetrabenzo-3,7,9,13,17,19-hexadehydro[20]annulene: Formation of Onion- and Tube-like Closed-Shell Carbon Particles , 1997 .

[18]  Jin Zhai,et al.  Creation of a superhydrophobic surface from an amphiphilic polymer. , 2003, Angewandte Chemie.

[19]  M. R. Freeman,et al.  Direct Writing of Patterned Ceramics Using Electron‐Beam Lithography and Metallopolymer Resists , 2004 .

[20]  Uwe H. F. Bunz,et al.  Polymere mit komplexierten Cyclobutadieneinheiten in der Hauptkette; das erste Beispiel eines thermotropen, flüssigkristallinen, metallorganischen Polymers , 1995 .

[21]  Frank Caruso,et al.  Gold-silica inverse opals by colloidal crystal templating , 2002 .

[22]  Orlin D. Velev,et al.  Structured porous materials via colloidal crystal templating: from inorganic oxides to metals , 2000 .

[23]  A. Kiennemann,et al.  Preparation and characterization of Fischer-Tropsch active Co/SiO2 catalysts , 1999 .

[24]  K. Sonogashira,et al.  Development of Pd–Cu catalyzed cross-coupling of terminal acetylenes with sp2-carbon halides , 2002 .

[25]  Jane F. Bertone,et al.  A lost-wax approach to monodisperse colloids and their crystals. , 2001, Science.

[26]  U. Bunz,et al.  POLYMERS WITH COMPLEXED CYCLOBUTADIENE UNITS IN THE MAIN-CHAIN - THE FIRST EXAMPLE OF A THERMOTROPIC, LIQUID-CRYSTALLINE ORGANOMETALLIC POLYMER , 1995 .

[27]  Martina H. Stenzel,et al.  Formation of Regular Honeycomb-Patterned Porous Film by Self-Organization , 2002 .

[28]  C. Knobler,et al.  Growth of Breath Figures on Fluid Surfaces , 1988 .

[29]  Chung-Yuan Mou,et al.  Fabrication of Tunable Superhydrophobic Surfaces by Nanosphere Lithography , 2004 .

[30]  C. Barner‐Kowollik,et al.  Nano- and micro-engineering of ordered porous blue-light-emitting films by templating well-defined organic polymers around condensing water droplets. , 2003, Angewandte Chemie.

[31]  U. Bunz,et al.  Synthesis of novel polymers containing cyclobutadiene thiophene and alkyne units: polymeric organometallic mesogens , 1995 .

[32]  Eric van Steen,et al.  TPR Study on the Preparation of Impregnated Co/SiO2Catalysts , 1996 .

[33]  S. Jenekhe,et al.  Self-assembled aggregates of rod-coil block copolymers and their solubilization and encapsulation of fullerenes , 1998, Science.

[34]  K. Vollhardt,et al.  The diethynylcyclobutadiene rearrangement: a degenerate ligand reorganization in the coordination sphere of (.eta.5-cyclopentadienyl)cobalt , 1982 .

[35]  S. Jenekhe,et al.  Self-assembly of ordered microporous materials from rod-coil block copolymers , 1999, Science.

[36]  A. Stein Sphere templating methods for periodic porous solids , 2001 .

[37]  Georges Hadziioannou,et al.  Microporous honeycomb-structured films of semiconducting block copolymers and their use as patterned templates , 2000 .

[38]  E. H. Barton Smoke Trace of Compound Vibrations of Tuning-fork. , 1912, Nature.

[39]  René Wilhelm,et al.  Near-quantitative solid-state synthesis of carbon nanotubes from homogeneous diphenylethynecobalt and -nickel complexes. , 2003, Angewandte Chemie.

[40]  U. Scherf,et al.  Conjugated organometallic polymers containing Vollhardt's cyclobutadiene complex: aggregation and morphologies. , 2001, Chemistry.

[41]  D. C. Bradley Metal alkoxides as precursors for electronic and ceramic materials , 1989 .

[42]  S. Jenekhe,et al.  Supramolecular Self-Assembly of Three-Dimensional Nanostructures and Microstructures: Microcapsules from Electroactive and Photoactive Rod−Coil−Rod Triblock Copolymers , 2000 .

[43]  Mohan Srinivasarao,et al.  Three-Dimensionally Ordered Array of Air Bubbles in a Polymer Film , 2001, Science.

[44]  Bernard François,et al.  Self-organized honeycomb morphology of star-polymer polystyrene films , 1994, Nature.