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Crystal structure of a binuclear mixed-valence ytterbium complex containing a 2-anthracene-substituted phenoxide ligand.

ABSTRACT: Reaction of 2-(anthracen-9-yl)phenol (HOPhAn, 1) with divalent Yb[N(SiMe₃)₂]₂·2THF in THF-toluene mixtures affords the mixed-valence Yb^II-Yb^III dimer {[2-(anthracen-9-yl)phenolato-?O]bis-(tetra-hydro-furan)-ytterbium(III)}-tris-[?-2-(anthracen-9-yl)phenolato]-?⁴ O:O;?O:1,2-?,?O-{[2-(anthracen-9-yl)phenolato-?O]ytterbium(II)} toluene tris-olvate, [Yb₂(C₂₀H₁₃O)₅(C₄H₈O)₂]·3C₇H₇ or [Yb^III(THF)₂(OPhAn)](?-OPhAn)₃[Yb^II(OPhAn)]·3C₇H₇ (2), as the major product. It crystallized as a toluene tris-olvate. The Yb-O bond lengths in the crystal structure of this dimer clearly identify the Yb^II and Yb^III centres. Inter-estingly, the formally four-coordinate Yb^II centre shows a close contact with one anthracene C-C bond of a bridging OPhAn ligand, bringing the formal coordination number to five.

SUBMITTER: Berg DJ

PROVIDER: S-EPMC6727046 | biostudies-literature | 2019 Sep

REPOSITORIES: biostudies-literature

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Crystal structure of a binuclear mixed-valence ytterbium complex containing a 2-anthracene-substituted phenoxide ligand.

Berg David J DJ Twamley Brendan B

Acta crystallographica. Section E, Crystallographic communications 20190823 Pt 9

Reaction of 2-(anthracen-9-yl)phenol (HOPhAn, 1) with divalent Yb[N(SiMe3)2]2·2THF in THF-toluene mixtures affords the mixed-valence YbII-YbIII dimer {[2-(anthracen-9-yl)phenolato-κO]bis-(tetra-hydro-furan)-ytterbium(III)}-tris-[μ-2-(anthracen-9-yl)phenolato]-κ4 O:O;κO:1,2-η,κO-{[2-(anthracen-9-yl)phenolato-κO]ytterbium(II)} toluene tris-olvate, [Yb2(C20H1 ...[more]

PMID: 31523468

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Project description:Two mononuclear and one binuclear ytterbium complexes with dual near-infrared (NIR) photoluminescence and reversible trans-to-cis photoisomerization functions were synthesized and characterized. The central ytterbium(III) ion coordinates with two β-diketonate (4,4,4-trifluoro-1-phenylbutane-1,3-dionate (tfd)) ligands and one deprotonated azobenzene-containing tetradentate ligand [(E)-4-(phenyldiazenyl)-N,N-bis(pyridin-2-ylmethyl) benzohydrazide (HL), (E)-4-((4-(dimethylamino)phenyl)diazenyl)-N,N-bis(pyridin-2-ylmethyl)benzohydrazide (HNL), or (E)-4,4'-N',N'-bis(pyridin-2-ylmethyl)benzohydrazide azobenzene (H2DL)] to form a neutral ternary complex ([Yb(tfd)2L], [Yb(tfd)2(NL)], or [Yb2(tfd)4(DL)], respectively), where the ytterbium(III) ion is eight-coordinated to N3O5 donor sets. X-ray crystallographic analysis shows that all three complexes form a trigonal dodecahedron geometry with similar -N=N- distances that are slightly longer than those of the pure azobenzene-containing ligands. The NIR luminescence properties of the Yb(III) complexes were determined at a wavelength of about 980 nm with quantum yields in the range of 0.4-0.6% in ethanol and acetonitrile solutions at room temperature, and trans-to-cis photoisomerization was determined with the quantum yields (Φt→c = 10-2) at the same level as their pure ligands. The trans-to-cis photoisomerization rates of the complexes (10-4 s-1) are slightly higher than those of the pure ligands and similar to azobenzene (10-5 to 10-4 s-1). From time-dependent density functional theory calculations of the energy levels of the first excited triplet states of the ligands, the energies of the lowest excited triplet states of all of the ligands are higher than the resonance level of Yb3+ (2F5/2, 1.2722 eV). We suggest that these azo-containing ligands may participate in energy transfer to the ytterbium ion, in addition to the main "antenna effect" ligand tfd. This is the first report of azobenzene group-functionalized ytterbium complexes with dual NIR luminescence and photoisomerization properties, indicating that azobenzene-containing lanthanide(III) complexes have potential applications as dual function materials in biological systems.

Dataset Information

Crystal structure of a binuclear mixed-valence ytterbium complex containing a 2-anthracene-substituted phenoxide ligand.

Publications

Crystal structure of a binuclear mixed-valence ytterbium complex containing a 2-anthracene-substituted phenoxide ligand.

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