TY - JOUR
T1 - Design and Modulation of Selectivity toward Vanadium(V) and Uranium(VI) Ions
T2 - Coordination Properties and Affinity of Hydroxylamino-Triazine Siderophores
AU - Amoiridis, Angelos
AU - Papanikolaou, Michael
AU - Vlasiou, Manolis
AU - Bandeira, Nuno A.G.
AU - Miras, Haralampos N.
AU - Kabanos, Themistoklis
AU - Keramidas, Anastasios
N1 - Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society.
PY - 2023/12/11
Y1 - 2023/12/11
N2 - Based on the strong binding and high selectivity properties of 2,6-bis[hydroxy(methyl)amino]-4-morpholino-1,3,5-triazine (H2bihyat) for [UVIO2]2+, novel binucleating ligands (BLs) N,N′,N″,N‴-((1,4-phenylenebis(oxy))bis(1,3,5-triazine-6,2,4-triyl))tetrakis(N-methylhydroxylamine) (H4qtn), N1,N4-bis(4,6-bis(hydroxy(methyl)amino)-1,3,5-triazin-2-yl)benzene-1,4-diamine (H4pdl), and N1,N2-bis(4,6-bis(hydroxy(methyl)amino)-1,3,5-triazin-2-yl)ethane-1,2-diamine (H4enl) were synthesized. Binuclear complexes formed by coordination of hard metal ions with H4qtn are thermodynamically more stable than their mononuclear analogues with H2bihyat due to the increase in entropy accompanying the formation of more chelate rings. Reaction of either H4qtn or H4pdl or H4enl with [UVIO2]2+ and [VVO2]+ resulted in the isolation of the binuclear complexes [(UVIO2)2(μ-qtn)(H2O)4] (1), [(VVO2)2(μ-qtn)][PPh4]2[PPh4] (2), [(UVIO2)2(μ-pdl)(H2O)2(MeOH)2] (3), [(VVO2)2(μ-pdl)][PPh4]2 (4), [(UVIO2)2(μ-enl)(H2O)4] (5), and [(VVO2)2(μ-enl)][PPh4]2 (6). The binuclear complexes 1-6 were characterized by single-crystal X-ray diffraction analysis in solid state and by NMR and ESI-MS in solution. The comparison of the coordination ability of the BLs with either pyridine-2,6-dicarboxylic acid (H2dipic) or H2bihyat or CO32- toward [UVIO2]2+ and [VVO2]+ was investigated by NMR and UV-vis spectroscopies and DFT theoretical calculations, revealing a superior performance of BLs. The selectivity of the BLs for [UVIO2]2+ over [VVO2]+ is decreased compared to that of H2bihyat but increases considerably at pH > 9 values. Formation of the mixed-metal binuclear species [UVIO2(μ-O)VVO2] influences the selectivity and dynamics of the reaction of H4qtn for [UVIO2]2+ and [VVO2]+ in aqueous solution. The results of this study provide crucial information for the ligand design and the development of stronger and more selective systems.
AB - Based on the strong binding and high selectivity properties of 2,6-bis[hydroxy(methyl)amino]-4-morpholino-1,3,5-triazine (H2bihyat) for [UVIO2]2+, novel binucleating ligands (BLs) N,N′,N″,N‴-((1,4-phenylenebis(oxy))bis(1,3,5-triazine-6,2,4-triyl))tetrakis(N-methylhydroxylamine) (H4qtn), N1,N4-bis(4,6-bis(hydroxy(methyl)amino)-1,3,5-triazin-2-yl)benzene-1,4-diamine (H4pdl), and N1,N2-bis(4,6-bis(hydroxy(methyl)amino)-1,3,5-triazin-2-yl)ethane-1,2-diamine (H4enl) were synthesized. Binuclear complexes formed by coordination of hard metal ions with H4qtn are thermodynamically more stable than their mononuclear analogues with H2bihyat due to the increase in entropy accompanying the formation of more chelate rings. Reaction of either H4qtn or H4pdl or H4enl with [UVIO2]2+ and [VVO2]+ resulted in the isolation of the binuclear complexes [(UVIO2)2(μ-qtn)(H2O)4] (1), [(VVO2)2(μ-qtn)][PPh4]2[PPh4] (2), [(UVIO2)2(μ-pdl)(H2O)2(MeOH)2] (3), [(VVO2)2(μ-pdl)][PPh4]2 (4), [(UVIO2)2(μ-enl)(H2O)4] (5), and [(VVO2)2(μ-enl)][PPh4]2 (6). The binuclear complexes 1-6 were characterized by single-crystal X-ray diffraction analysis in solid state and by NMR and ESI-MS in solution. The comparison of the coordination ability of the BLs with either pyridine-2,6-dicarboxylic acid (H2dipic) or H2bihyat or CO32- toward [UVIO2]2+ and [VVO2]+ was investigated by NMR and UV-vis spectroscopies and DFT theoretical calculations, revealing a superior performance of BLs. The selectivity of the BLs for [UVIO2]2+ over [VVO2]+ is decreased compared to that of H2bihyat but increases considerably at pH > 9 values. Formation of the mixed-metal binuclear species [UVIO2(μ-O)VVO2] influences the selectivity and dynamics of the reaction of H4qtn for [UVIO2]2+ and [VVO2]+ in aqueous solution. The results of this study provide crucial information for the ligand design and the development of stronger and more selective systems.
UR - http://www.scopus.com/inward/record.url?scp=85179603088&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.3c02678
DO - 10.1021/acs.inorgchem.3c02678
M3 - Article
C2 - 38018803
AN - SCOPUS:85179603088
SN - 0020-1669
VL - 62
SP - 19971
EP - 19985
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 49
ER -