Tuning the structure and Zn(ii) sensing of lanthanide complexes with two phenylimidazophenanthrolines by acetonitrile hydrolysis

Abstract

1D/0D lanthanide complexes of phenylimidazophenanthrolines were constructedviahydrolysis of acetonitrile, and0-Eushows prompt photoemission response to Zn2+.

Dinuclear Lanthanide(III) Complexes from the Use of Methyl 2-Pyridyl Ketoxime: Synthetic, Structural, and Physical Studies

“…To the best of our knowledge, the present work represents the second case in which an Ln(III)-mediated hydrolysis of MeCN is experimentally observed. The first case involved the reactions of hydrated lanthanide(III) nitrates with 2-(4-carboxyphenyl)imidazo[4,5- f ][1–10]phenanthroline (Hcpip) and 2-phenylimidazo [4,5- f ][1–10]phenanthroline (pip) in MeCN/H 2 O under solvothermal conditions (~190 °C), which gave the 1D coordination polymers {[Ln 2 (O 2 CMe) 4 (cpip) 2 ]} n (Ln = Sm, Eu) and the dinuclear complexes [Ln 2 (O 2 CMe) 6 (pip) 2 ], respectively [ 54 ]. In the present case, the produced MeCO 2 H is neutralized by the also generated ammonia giving the acetato ligands and providing ammonium cations that provide charge balance for the released nitrate ions, Equation (1).…”

“…For a given bond, the Ln-O/N bond lengths follow the Nd>Dy order ( Table 1 ) due to lanthanide contraction; this trend is also observed for the Ln III… Ln III distances. The Ln-O/N bond lengths in 1 and 5 are typical for 9-coordinate Nd(III) [ 33 , 56 , 57 ] and Dy(III) [ 35 , 38 , 41 , 54 , 58 , 59 , 60 , 61 , 62 ]. The Ln1/Ln1′ coordination geometry was evaluated using the program SHAPE [ 61 , 63 ] and is best described as muffin-type ( Figure S1, Table S2 ); an alternative description of the polyhedron could be that of a spherical-capped square antiprism.…”

“…Complexes 1 , 5, and 6 are members of a rather large family of dinuclear complexes containing the {Ln 2 ( η 1 : η 1 : μ 2 -O 2 CMe) 2 ( η 1 : η 2 : μ 2 -O 2 CMe) 2 } 2+ unit [ 39 , 54 , 56 , 57 , 58 , 59 , 60 , 64 , 65 , 66 ]; (only representative references are given), most of which [ 54 , 58 , 60 , 64 , 65 ] contain an extra chelating acetato group per Ln III center; complexes containing a chelating nitrato group per Ln III atom, i.e., the unit {Ln 2 ( η 1 : η 1 : μ 2 -O 2 CMe) 2 ( η 1 : η 2 : μ 2 -O 2 CMe) 2 -( η 2 -OOΝO)}, are few [ 39 , 56 , 59 , 66 ].…”

“…To the best of our knowledge, the present work represents the second case in which an Ln(III)-mediated hydrolysis of MeCN is experimentally observed. The first case involved the reactions of hydrated lanthanide(III) nitrates with 2-(4-carboxyphenyl)imidazo [4,5- [54]. In the present case, the produced MeCO 2 H is neutralized by the also generated ammonia giving the acetato ligands and providing ammonium cations that provide charge balance for the released nitrate ions, Equation (1).…”

“…Ln III distances. The Ln-O/N bond lengths in 1 and 5 are typical for 9-coordinate Nd(III) [33,56,57] and Dy(III) [35,38,41,54,[58][59][60][61][62]. The Ln1/Ln1 coordination geometry was evaluated using the program SHAPE [61,63] and is best described as muffin-type (Figure S1, Table S2); an alternative description of the polyhedron could be that of a spherical-capped square antiprism.…”