Highly Metallized Polymers:  Synthesis, Characterization, and Lithographic Patterning of Polyferrocenylsilanes with Pendant Cobalt, Molybdenum, and Nickel Cluster Substituents

Abstract

High molecular weight, soluble, air- and moisture-stable, highly metallized (>25 wt% metal) polyferrocenylsilanes (PFS) [Fe(eta-C5H4)2Si(Me){Co2(CO)6C2Ph}]n (Co-PFS), [Fe(eta-C5H4)2Si(Me){Mo2-Cp2(CO)4C2Ph}]n (Mo-PFS), and [Fe(eta-C5H4)2Si(Me){Ni2Cp2C2Ph}]n (Ni-PFS) containing pendant cobalt, molybdenum, and nickel clusters, respectively, have been prepared via macromolecular clusterization of an acetylide-substituted PFS [Fe(eta-C5H4)2Si(Me)C(triple bond)CPh]n with [Co(2)(CO)8], [{MoCp(CO)(2)}2], or [{NiCp(CO)}2]. The extent of clusterization achieved was in the range of 70-75%. All three highly metallized polymers were demonstrated to function as negative-tone resists in electron-beam lithography, while Co-PFS and Mo-PFS were successfully patterned by UV-photolithography, allowing the fabrication of micron-sized bars, dots, and lines. These studies suggest that the highly metallized polymers may be useful in the fabrication of patterned arrays of alloy nanoparticles for both materials science and catalytic applications.

Strained Metallocenophanes and Related Organometallic Rings Containing π‐Hydrocarbon Ligands and Transition‐Metal Centers

“…[79,80] After polymerization and subsequent introduction of the metal fragments, clusterized bimetallic polymers with high metal content are obtained, which are suited for applications as resists for electronbeam and UV photolithography. [81] The first spirocyclic [1]ferrocenophane 18 was reported in 1975 by Osborne and Whiteley [5a] in 7 % yield from the reaction of dilithioferrocene with SiCl 4 . Preparation of 18 in higher yield (which allowed for Scheme 2.…”

Synthesis, photochemistry, and electrochemistry of ruthenium(II) polypyridyl complexes anchored by dicobalt carbonyl units

“…Orange precipitates 3 and 4 were collected by filtration. The Ru-Co 2 heteronuclear hybrid complexes, [Ru(bpy) 2 -{phen-C{Co 2 (CO) 4 (dppm)}C-tolyl}](PF 6 ) 2 (1) and [Ru(bpy) 2 {tolyl-C{Co 2 (CO) 4 (dppm)}C-phen-C{Co 2 (CO) 4 -(dppm)}C-tolyl}](PF 6 ) 2 (2), were synthesized from ruthenium complex 3 or 4 and Co 2 (CO) 6 (dppm) (dppm = bis(diphenylphsphino)methane) and were obtained in good yields. Novel Ru-Co 2 complexes 1 and 2 were characterized by IR, UV-Vis, ESI-mass spectroscopies, and elemental analysis.…”

“…The solution was left standing for 24 h after the electrolysis was turned off. 2 {phen-C{Co 2 (CO) 4 (dppm)}-C-tolyl}](PF 6 ) 2 (1)…”

“…Growing interest has focused on the useful properties and applications of dicobalt carbonyl derivatives to organometallic chemistry as metallodendrimers [1][2][3] and to synthetic chemistry for developing the Pauson-Khand reaction [4][5][6][7]. Recent studies on heteronuclear metal complexes and clusters containing dicobalt carbonyl organometallics, M-Co 2 (M = Pd, Ru, Fe, Co, etc.…”

“…These combined systems have exhibited emission quenching by an intramolecular energy transfer from the ruthenium polypyridyl unit to the manganese moiety under many circumstances. Recently, ruthenium polypyridyl complexes containing a bipyridine or phenanthroline ligand with ethynylarene substituents, Ru-(bpy) 2 these complexes to opt-electronic materials have been clarified [16][17][18]. This type of ruthenium complex is a good candidate for the construction of a hybrid system with the dicobalt carbonyl derivatives mentioned above.…”