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Dibismuthates as Linking Units for Bis-Zwitterions and Coordination Polymers.

ABSTRACT: Adducts of bismuth trihalides BiX3 (X = Cl, Br, I) and the PS3 ligand (PS3 = P(C6H4-o-CH2SCH3)3) react with HCl to form inorganic/organic hybrids with the general formula [HPS3BiX4]2. On the basis of their solid-state structures determined by single-crystal X-ray diffraction, these compounds exhibit discrete bis-zwitterionic assemblies consisting of two phosphonium units [HPS3]+ linked to a central dibismuthate core [Bi2X8]2- via S?Bi dative interactions. Remarkably, the phosphorus center of the PS3 ligand undergoes protonation with hydrochloric acid. This is in stark contrast to the protonation of phosphines commonly observed with hydrogen halides resulting in equilibrium. To understand the important factors in this protonation reaction, 31P NMR experiments and DFT computations have been performed. Furthermore, the dibismuthate linker was utilized to obtain the coordination polymer {[AgPS3BiCl3(OTf)]2(CH3CN)2}?, in which dicationic [Ag(PS3)]22+ macrocycles containing five-coordinate silver centers connect the dianionic [Bi2Cl6(OTf)2]2- dibismuthate fragments. The bonding situation in these dibismuthates has been investigated by single-crystal X-ray diffraction and DFT calculations (NBO analysis, AIM analysis, charge distribution).

SUBMITTER: Fekete C

PROVIDER: S-EPMC7509842 | biostudies-literature | 2020 Sep

REPOSITORIES: biostudies-literature

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Dibismuthates as Linking Units for Bis-Zwitterions and Coordination Polymers.

Fekete Csilla C Barrett Jamie J Benkő Zoltán Z Heift Dominikus D

Inorganic chemistry 20200908 18

Adducts of bismuth trihalides BiX3 (X = Cl, Br, I) and the PS3 ligand (PS3 = P(C6H4-o-CH2SCH3)3) react with HCl to form inorganic/organic hybrids with the general formula [HPS3BiX4]2. On the basis of their solid-state structures determined by single-crystal X-ray diffraction, these compounds exhibit discrete bis-zwitterionic ass ...[more]

PMID: 32897714

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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.

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Dibismuthates as Linking Units for Bis-Zwitterions and Coordination Polymers.

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Dibismuthates as Linking Units for Bis-Zwitterions and Coordination Polymers.

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