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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) 5 Cr(η 1 -2-isocyano-1,3-diethoxycarbonyl-6-mercaptoazulene)] ( 7 ) with Ph 3 PAuCl, under basic conditions, afforded X-ray structurally characterized heterobimetallic Cr 0 /Au I ensemble [(OC) 5 Cr(μ-η 1 :η 1 -2-isocyano-1,3-diethoxycarbonyl-6-azulenylthiolate)AuPPh 3 ] ( 8 ). Analysis of the 13 C NMR chemical shifts for the [(NC)Cr(CO) 5 ] core in a series of the related complexes [(OC) 5 Cr(2-isocyano-6-X-1,3-diethoxy-carbonylazulene)] (X = -N≡C, Br,H, SH, SCH 2 CH 2 CO 2 CH 2 CH 3 , SAuPPh 3 ) unveiled remarkably consistent inverse-linear correlations δ(  13 C O trans ) vs. δ(  13 C N) and δ(  13 C O cis ) vs. δ(  13 C N) that appear to hold well beyond the above 2-isocyanoazulenic series to include complexes [(OC) 5 Cr(CNR)] containing strongly electron-withdrawing substituents R, such as CF 3 , CFClCF 2 Cl, C 2 F 3 , and C 6 F 5 . In addition to functioning as asensitive 13 C NMR handle, the essentially C 4v -symmetric [(-NC)Cr(CO) 5 ] moiety proved to be an informative, remote, ν N≡C /ν C≡O infrared reporter in probing chemisorption of 7 on the Au(111) surface.

chemical science

First π-linker featuring mercapto and isocyano anchoring groups within the same molecule: synthesis, heterobimetallic complexation and self-assembly on Au(111)