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Bis(dipyrrinato)metal(ii) coordination polymers: crystallization, exfoliation into single wires, and electric conversion ability.

ABSTRACT: One-dimensional coordination polymers (1D-CPs) tend either to dissociate into constitutive ligands and metals readily in solution, or to aggregate randomly and amorphously, which prevents them from widespread application. In the present research, 1D-CPs comprising bridging dipyrrin ligands and divalent metal ions (Zn²⁺, Ni²⁺, and Cu²⁺) are synthesized. A liquid/liquid interfacial reaction gives rise to single crystals suitable for X-ray diffraction analysis: A dichloromethane solution of the ligand is layered with aqueous metal(ii) acetate, such that the coordination reaction proceeds at the liquid/liquid interface. Isolated single fibers of the zinc coordination polymer may be exfoliated from the single crystal or bulk solid upon ultrasonication. Atomic force microscopy (AFM) detects the isolated fibers with lengths of more than several ?m. The exfoliated 1D-CP wires feature good processability, realizing a conjugate with single-wall carbon nanotubes (SWCNTs), and a thin film on a transparent SnO₂ electrode. The processed materials show electric conversion ability: For example, the modified SnO₂ electrode serves as a photoanode for a photoelectric conversion system. The designability and tunability of the present 1D-CPs is demonstrated by a ligand modification, affording a luminescent property and an extension of the photoelectric conversion response to longer wavelengths.

SUBMITTER: Matsuoka R

PROVIDER: S-EPMC5489023 | biostudies-literature | 2015 May

REPOSITORIES: biostudies-literature

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Bis(dipyrrinato)metal(ii) coordination polymers: crystallization, exfoliation into single wires, and electric conversion ability.

Matsuoka Ryota R Toyoda Ryojun R Sakamoto Ryota R Tsuchiya Mizuho M Hoshiko Ken K Nagayama Tatsuhiro T Nonoguchi Yoshiyuki Y Sugimoto Kunihisa K Nishibori Eiji E Kawai Tsuyoshi T Nishihara Hiroshi H

Chemical science 20150226 5

One-dimensional coordination polymers (1D-CPs) tend either to dissociate into constitutive ligands and metals readily in solution, or to aggregate randomly and amorphously, which prevents them from widespread application. In the present research, 1D-CPs comprising bridging dipyrrin ligands and divalent metal ions (Zn2+, Ni2+, and Cu2+) are synthesized. A liquid/liquid interfacial reaction gives rise to single crystals suitable for X-ray diffraction analysis: A di ...[more]

PMID: 28706672

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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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Bis(dipyrrinato)metal(ii) coordination polymers: crystallization, exfoliation into single wires, and electric conversion ability.

Publications

Bis(dipyrrinato)metal(ii) coordination polymers: crystallization, exfoliation into single wires, and electric conversion ability.

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