A bifunctional 2,2 ':6 ',2 ''-terpyridine-based ligand for ratiometric Cu(II) sensing

作者：Abdalrahman M A; Abebe F; Briggs J; Kassel W S; Burdette S C; Seitz W R; Pl****p R P^*

来源：Journal of Coordination Chemistry, 2017, 70(7): 1123-1136.

DOI：10.1080/00958972.2017.1300660

• Copper(II) sensing
• bifunctional ligand
• ratiometric sensor
• poly(N-isopropylacrylamide)
• job's plot

Synthesis and characterization of the bifunctional sensor receptor ligand N-([2,2':6',2 ''-terpyridine]-4'-yl)methyl)-N-propylacrylamide (1) and the model ligand N-([2,2':6',2 ''-terpyridine]-4'-yl)methyl)-N-propylisobutyramide (2) are described. Ligand 1 is a receptor for Cu(II) that is copolymerizable with N-isopropylacrylamide giving a ratiometric sensor of weakly bound Cu(II) in environmental waters. Ligand 2 is a model for copolymerized 1 whereby the reactive acrylamide group is replaced by isobutyramide. Solution speciation of complexes of Cu(II) and Zn(II) with 2 were investigated spectroscopically and their solid-state structures were studied through single-crystal X-ray diffraction. Solution UV-vis and fluorescence studies show a preference of 2 toward Cu(II) over Na(I), Zn(II), Cu(II), Co(II), Mn(II), Ni(II), Cd(II), and Pb(II) in accord with the Irving-Williams series and other coordination principles. Solution speciation determined in a weakly coordinating aqueous-organic (60 : 40 DMF/H2O) medium indicates 1 : 1 Cu(II): 2 binding as desired in that formation of [Cu(2)(2)](2+) would crosslink the polymer sensor. The crystal structures of [Cu(2)(NO3)(2)] and [Zn(2)(NO3)(2)]center dot MeOH center dot 1/2Et(2)O display distorted octahedral geometries where 2 coordinates meridionally and two nitrate groups occupy the remaining sites around the metal center.
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• 出版日期2017