Abstract: Structure-dependent photoluminescence was studied for lanthanide complexes with widespread Nacnac ligands, supplemented by thiolates; notable antenna properties of the latter are revealed. The range of lanthanide complexes with bulky N , N ′-bis(Dipp)-substituted β-diketiminate ligand Nacnac − = CH(CMe(NDipp)) 2 − (Dipp = 2,6-diisopropylphenyl) has been expanded to the complexes [Ln(Nacnac)I 2 (thf) n ] ( 1Ln , Ln = Gd , Tb , n = 2; Dy , n = 1; thf = tetrahydrofuran). They were further used in salt metathesis reactions with KSPh and KS(2-Py) (2-Py = 2-pyridyl), resulting in thiolato complexes [Ln(Nacnac)(SPh) 2 (thf)] ( 2Ln ) and [Ln(Nacnac)(SPy) 2 ] ( 3Ln ). As an analogue of 2Tb without coordinated thf molecules, binuclear complex [{Tb(Nacnac)(SPh)} 2 (μ-SPh) 2 ] ( 4Tb ) was obtained by reaction of dry TbI 3 with K(Nacnac) and KSPh in Et 2 O followed by recrystallization from toluene. The diiodo complexes possess different numbers of coordinated thf molecules and different coordination polyhedra owing to the lanthanide contraction. On the contrary, all 2Ln and 3Ln have the same molecular and crystal structures for a given thiolate, owing to the coordination rigidity provided by edge coordination of a Ph cycle or by chelating binding of a S(2-Py) − ligand. UV-vis and photoluminescence spectra were registered for all compounds. A triplet level of the Nacnac − ligand of 2.22 × 10 4 cm −1 was determined from the solid-state emission of Gd complex 1Gd at 77 K; the triplet level in 2Gd and 3Gd was found at 2.16 × 10 4 cm −1 . Emission lifetimes and quantum yields were measured for all Tb compounds with the highest values for thiolato complexes 2Tb and 3Tb , while 1Tb showed only weak emission. The relationship of the emission properties with the molecular and crystal structures is discussed, and better antenna properties are proposed for thiolato rather than for Nacnac − ligands.

Cite: Mironova O.A. , Pyadun A.A. , Sukhikh T.S. , Konchenko S.N. , Pushkarevsky N.A.
Synthesis and luminescence studies of lanthanide complexes (Gd, Tb, Dy) with phenyl- and 2-pyridylthiolates supported by a bulky β-diketiminate ligand. Impact of the ligand environment on terbium(III) emission
New Journal of Chemistry. 2020. V.44. N45. P.19769-19779. DOI: 10.1039/d0nj04201c WOS Scopus РИНЦ OpenAlex

Dates:

Submitted:	Aug 20, 2020
Accepted:	Oct 19, 2020

Identifiers:

Web of science:	WOS:000594503300032
Scopus:	2-s2.0-85096962588
Elibrary:	45113207
OpenAlex:	W3093828588

Citing:

DB	Citing
OpenAlex	13
Web of science	11
Scopus	11
Elibrary	13

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