Mercapto (-SH) and isocyano (-N≡C) terminated conducting π-linkers are often employed in the ever-growing quest for organoelectronic materials. While such systems typically involve symmetric dimercapto or diisocyano anchoring of the organic bridge, this article introduces the chemistry of a linear azulenic π-linker equipped with one mercapto and one isocyano terminus. The 2-isocyano-6-mercaptoazulene platform was efficiently accessed from 2-amino-6-bromo-1,3-diethoxycarbonylazulene in four steps. The 2-N≡C end of this 2,6-azulenic motif was anchrored to the [Cr(CO)5] fragment prior to formation of its 6-SH terminus. Metalation of the 6-SH end of [(OC)5Cr(η1-2-isocyano-1,3-diethoxycarbonyl-6-mercaptoazulene)] (7) with Ph3PAuCl, under basic conditions, afforded X-ray structurally characterized heterobimetallic Cr0/AuI ensemble [(OC)5Cr(μ-η1:η1-2-isocyano-1,3-diethoxycarbonyl-6-azulenylthiolate)AuPPh3] (8). Analysis of the 13C NMR chemical shifts for the [(NC)Cr(CO)5] core in a series of the related complexes [(OC)5Cr(2-isocyano-6-X-1,3-diethoxy-carbonylazulene)] (X = -N≡C, Br,H, SH, SCH2CH2CO2CH2CH3, SAuPPh3) unveiled remarkably consistent inverse-linear correlations δ(13COtrans) vs. δ(13CN) and δ(13COcis) vs. δ(13CN) that appear to hold well beyond the above 2-isocyanoazulenic series to include complexes [(OC)5Cr(CNR)] containing strongly electron-withdrawing substituents R, such as CF3, CFClCF2Cl, C2F3, and C6F5. In addition to functioning as asensitive 13C NMR handle, the essentially C4v-symmetric [(-NC)Cr(CO)5] moiety proved to be an informative, remote, νN≡C/νC≡O infrared reporter in probing chemisorption of 7 on the Au(111) surface.

Atomic force microscopy (AFM) tip-based fabrication has gained attention due to its unparalleled precision and control for designing nano-and microscale features. Such features have utility in applications including miniaturized electronics, biological sensing, and plasmonics. Herein, we discuss an AFM tip-based plowing approach to create patterns on the micron scale in a thin CaCO 3 nanoparticle (NP) film, deposited over a wide range of substrates. The CaCO 3 NP layer's high thermal stability allows it to be used as a resist film during high vacuum thermal evaporation of gold. After metal deposition, the NP resist film is selectively removed in aqueous solutions either by complexing with ethylenediaminetetraacetic acid or by dissolution with dilute HCl. The resulting gold metal features on surfaces were characterized by AFM and optical microscopy. The metal features were commensurate with the patterns created in the NP film. This fabrication approach was demonstrated on glass, Si, and mica, and the metal features show reasonable adhesion and stability. This patterning approach is unique in that it allows for the deposition of precisely placed metal microstructures with a defined size, shape, placement, and orientation on various substrates while using simple, easily removable resists. Salt-based resists can be removed in aqueous solutions with minimal contamination or damage to the metal features. This versatile method could be used to deposit fixed metal features on any desired substrate for applications from sensors to electronics. This is particularly useful for applications with conductive structures on optically transparent substrates, which are more challenging to fabricate with other approaches.