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Structural Diversity of Mercury(II) Halide Complexes Containing Bis-pyridyl-bis-amide with Bulky and Angular Backbones: Ligand Effect and Metal Sensing.

ABSTRACT: Hg(II) halide complexes [HgCl₂] 2L¹ [L¹ = N,N'-bis(3-pyridyl)bicyclo(2,2,2,)oct-7-ene-2,3,5,6-tetracarboxylic diamide), 1, [HgBr₂(L¹)]_n, 2, [HgI₂(L¹)], 3, [Hg₂X₄(L²)₂] [X = Cl, 4, Br, 5, and I, 6; L² = N,N'-bis(4-pyridylmethyl)bicyclo(2,2,2,)oct-7-ene-2,3,5,6-tetracarboxylic diamide] and {[HgX₂(L³)]⋅H₂O}_n [X = Cl, 7, Br, 8 and I, 9; L³ = 4,4'-oxybis(N-(pyridine-3-yl)benzamide)] are reported and structurally characterized using single-crystal X-ray diffraction analyses. The linear HgCl₂ units of complex 1 are interlinked by the L¹ ligands through Hg---N and Hg---O interactions, resulting in 1D supramolecular chains. Complex 2 shows 1D zigzag chains interlinked through the Br---Br interactions to form 1D looped supramolecular chains, while the mononuclear [HgI₂L²] molecules of 3 are interlinked through Hg---O and I---I interactions, forming 2D supramolecular layers. Complexes 4-6 are isomorphous dinuclear metallocycles, and 7-9 form isomorphous 1D zigzag chains. The roles of the ligand type and the halide anion in determining the structural diversity of 1-9 is discussed and the luminescent properties of 7-9 evaluated. Complexes 7-9 manifest stability in aqueous environments. Moreover, complexes 7 and 8 show good sensing towards Fe³⁺ ions with low detection limits and good reusability up to five cycles, revealing that the Hg-X---Fe³⁺ (X = Cl and Br) interaction may have an important role in determining the quenching effect of 7 and 8.

SUBMITTER: Govindaraj M

PROVIDER: S-EPMC9323401 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature

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Structural Diversity of Mercury(II) Halide Complexes Containing Bis-pyridyl-bis-amide with Bulky and Angular Backbones: Ligand Effect and Metal Sensing.

Govindaraj Manivannan M Huang Wei-Chun WC Lee Chia-Yi CY Lakshmanan Venkatesan V Liu Yu-Hsiang YH So Pamela Berilyn PB Lin Chia-Her CH Chen Jhy-Der JD

International journal of molecular sciences 20220716 14

Hg(II) halide complexes [HgCl2] 2L1 [L1 = N,N'-bis(3-pyridyl)bicyclo(2,2,2,)oct-7-ene-2,3,5,6-tetracarboxylic diamide), 1, [HgBr2(L1)]n, 2, [HgI2(L1)], 3, [Hg2X4(L2)2] [X = Cl, 4, Br, 5, and I, 6; L2 = N,N'-bis(4-pyridylmethyl)bicyclo(2,2,2,)oct-7-ene-2,3,5,6 ...[more]

PMID: 35887209

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Project description:Ten coordination polymers constructed from divalent metal salts, polycarboxylic acids, and bis-pyridyl-bis-amide ligands with different donor atom positions and flexibility are reported. They were structurally characterized by single-crystal X-ray diffraction. The ten coordination polymers are as follows: (1) {[Ni(L¹)(3,5-PDA)(H₂O)₃]·2H₂O}n (L¹ = N,N'-di(3-pyridyl)suberoamide, 3,5-H₂PDA = 3,5-pyridinedicarboxylic acid); (2) {[Ni₂(L¹)₂(1,3,5-HBTC)₂(H₂O)₄]·H₂O}n (1,3,5-H₃BTC = 1,3,5-benzenetricarboxylic acid); (3) {[Ni(L²)(5-tert-IPA)(H₂O)₂]·2H₂O}n (L² = N,N'-di(3-pyridyl)adipoamide, 5-tert-H₂IPA = 5-tert-butylisophthalic acid); (4) [Ni(L³)1.5(5-tert-IPA)]n (L³ = N,N'-di(4-pyridyl)adipoamide); (5) [Co(L¹)(1,3,5-HBTC)(H₂O)]n; (6) {[Co₃(L¹)₃(1,3,5-BTC)₂(H₂O)₂]·6H₂O}n; (7) [Cu(L⁴)(AIPA)]n (L⁴ = N,N'-bis(3-pyridinyl)terephthalamide, H₂AIPA = 5-acetamido isophthalic acid); (8) {[Cu(L²)0.5(AIPA)]·MeOH}n; (9) {[Zn(L⁴)(AIPA)]·2H₂O}n; and (10) {[Zn(L²)(AIPA)]·2H₂O}n. Complex 1 forms a 1D chain and 2 is a two-fold interpenetrated 2D layer with the sql topology, while 3 is a 2D layer with the hcp topology and 4 shows a self-catenated 3D framework with the rare (4²·6⁷·8)-hxg-d-5-C2/c topology. Different Co/1,3,5-H₃BTC ratios were used to prepare 5 and 6, affording a 2D layer with the sql topology and a 2D layer with the (4·8⁵)₂(4)₂(8³)₂(8) topology that can be further simplified to an hcp topology. While complex 7 is a 2D layer with the (4²·6⁷·8)(4²·6)-3,5L2 topology and 8 is a 2-fold interpenetrated 3D framework with the pcu topology, complexes 9 and 10 are self-catenated 3D frameworks with the (424·6⁴)-8T2 and the (4⁴·610·8)-mab topologies, respectively. The effects of the identity of the metal center, the ligand isomerism, and the flexibility of the spacer ligands on the structural diversity of these divalent coordination polymers are discussed. The luminescent properties of 9 and 10 and their photocatalytic effects on the degradation of dyes are also investigated.

Dataset Information

Structural Diversity of Mercury(II) Halide Complexes Containing Bis-pyridyl-bis-amide with Bulky and Angular Backbones: Ligand Effect and Metal Sensing.

Publications

Structural Diversity of Mercury(II) Halide Complexes Containing Bis-pyridyl-bis-amide with Bulky and Angular Backbones: Ligand Effect and Metal Sensing.

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