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Development of platforms capable of guarantee a controlled NO release at a specific target is highly promising yet challenging. Herein, we present the synthesis and characterization of cis-[Ru(bpy)2(1,4-dt)(NO)](PF6)3 (RuNO), where 1,4-dt = 1,4-dithiane and bpy = 2,2’-bipyridine, which was adsorbed on gold through the sulfur atom of 1,4-dt. This complex was thoroughly characterized by electrochemistry, nuclear magnetic resonance, and vibrational and electronic spectroscopies whose assignments were corroborated by theoretical data. The formation of the self-assembled monolayer (SAM) of RuNO on gold was monitored by surface plasmon resonance giving a coverage density of 2.1 × 10–10 mol cm–2. Taking advantage of the NO lability upon reduction, electrochemical scanning microscopy (SECM) was used to both trigger the NO release from the SAM of RuNO on the gold substrate and detection at the SECM tip. Accordingly, upon reduction, the generated NO0 species was detected at the SECM TIP, where it was oxidized back to NO+. challenging Herein cisRubpy21,4dtNOPF63 cisRubpy214dtNOPF63 cisRubpydtNOPF cis Ru 2 1,4 dt PF6 3 1 4 PF cis-[Ru(bpy)2(1,4-dt)(NO)](PF6) RuNO, , (RuNO) 1,4dt 14dt 1,4dithiane 14dithiane dithiane 2,2bipyridine, 22bipyridine bipyridine 2,2 bipyridine, 2,2’-bipyridine 1,4dt. dt. electrochemistry data selfassembled self assembled (SAM 21 2. 1010 10 10–1 cm2 cm cm–2 reduction (SECM tip Accordingly TIP NO+ cisRubpy21 4dtNOPF63 cisRubpy dtNOPF cisRubpy21,4dtNOPF6 cisRubpy214dtNOPF6 14 1, cis-[Ru(bpy)2(1,4-dt)(NO)](PF6 (RuNO 4dt 4dithiane 2bipyridine 2,2bipyridine 22 2, 101 10– cm– cisRubpy2 4dtNOPF6 cisRubpy21,4dtNOPF cisRubpy214dtNOPF cis-[Ru(bpy)2(1,4-dt)(NO)](PF 4dtNOPF