Highly photo- and triboluminescent lanthanide() coordination polymers based on diphosphine dioxides containing azaheterocyclic linkers

• Published in: New journal of chemistry 2023-05, Vol.47 (21), p.1446-1454
• Main Authors: Bryleva, Yuliya A, Komarov, Vladislav Yu, Glinskaya, Ludmila A, Artem'ev, Alexander V, Davydova, Maria P, Rakhmanova, Mariana I, Samsonenko, Denis G
• Format: Article
• Language: English
• Subjects: Ambient temperature; Chelation; Coordination polymers; Dioxides; Energy transfer; Ligands; Photoluminescence; Polyhedra; Polymers; Terbium; Thermal stability; Triboluminescence
• ISSN: 1144-0546; 1369-9261
• DOI: 10.1039/d3nj01119d

The reactions of Eu( iii ) and Tb( iii ) hexafluoroacetylacetonates (hfac − ) with 2,4-bis(diphenylphosphino)pyrimidine dioxide (L 1 ), 4,6-bis(diphenylphosphino)pyrimidine dioxide (L 2 ), or 3,6-bis(diphenylphosphino)pyridazine dioxide (L 3 ) afforded a new series of one-dimensional coordination polymers [LnL(hfac) 3 ] n (L = L 1 , L 2 , and L 3 ). Compounds [TbL 2 (hfac) 3 ] n and [LnL 3 (hfac) 3 ] n (Ln = Eu, Tb) consist of the eight-coordinated Ln( iii ) atoms linked by L 2 and L 3 ligands in the O , O ′-bridging manner (an O 8 polyhedron). In [LnL 1 (hfac) 3 ] n (Ln = Eu, Tb) and [EuL 2 (hfac) 3 ] n , one of the N atoms of bridging diphosphine dioxide is involved in the coordination to the Ln 3+ ion resulting in a N 1 O 8 polyhedron. All coordination polymers exhibit high thermal stability above 300 °C. The Eu( iii ) coordination polymers display strong photoluminescence with the solid-state quantum yield up to 61% observed for [EuL 1 (hfac) 3 ] n . The chelating coordination of L 1 and L 2 increases considerably the energy transfer efficiency from the ligands to Eu( iii ) compared to that of L 3 . The centrosymmetric coordination polymers [LnL 1 (hfac) 3 ] n exhibit strong triboluminescence that is clearly observed even in daylight at ambient temperature, while their non-centrosymmetric analogue [EuL 2 (hfac) 3 ] n displays lower triboluminescent activity, which is visible only in the dark. Six thermostable one-dimensional Eu 3+ and Tb 3+ coordination polymers constructed from diphosphine dioxides bearing azaheterocyclic linkers show bright photo- and triboluminescence.