Not Too Big and Not Too Small: “Goldilocks” Anion Size for Three-Dimensional Metal–Organic Frameworks Containing Oligothiophene Dinitrile Ligands (C4H2S)n(CN)2 (n = 1, 2, 3) Bridging Silver(I) Cations

Andreychuk, Nicholas R.; Allard, Sheena R.; Parent, Shawna L. M.; Assoud, Abdeljalil; MacKinnon, C.D.

doi:10.1021/acs.cgd.5b00698

Cited by 3 publications

(2 citation statements)

References 55 publications

(90 reference statements)

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“…In the presence of weakly coordinating anions such as BF 4 – or PF 6 – , however, the metal tends to satisfy its electronic requirements by binding to two N 2 systems and providing more varied molecular geometry, whose structural arrangements are driven by the aforementioned steric effect described in points (1)–(3). The combined effects of the anion properties and of the supramolecular interactions were investigated for other types of Ag(I) complexes, pointing to the strength of the metal-anion interaction , or anion size as key factors governing the overall architectures.…”

Section: Discussionmentioning

confidence: 99%

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Silver(I) and Thioether-bis(pyrazolyl)methane Ligands: The Correlation between Ligand Functionalization and Coordination Polymer Architecture

Bassanetti

Atzeri

Tinonin

et al. 2016

Crystal Growth & Design

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This work examines the crystal structures of 15 Ag(I) complexes with thioether functionalized bis(pyrazolyl)-methane derivatives to rationalize the influence of the ligand on the formation of (a) coordination polymers (CPs), (b) oligonuclear (hexameric and dinuclear) complexes, and (c) mononuclear complexes. It was previously reported how this ligand class could generate microporous architectures with permanent porosity. Some ligand modifications could induce a cavity size modulation while preserving the same overall architecture. The bis(pyrazolyl)methane scaffold can be easily functionalized with various structural fragments; hence the structural outcomes were studied in this work using various ligand modifications and Ag(I) salts. In particular, six new ligand classes were prepared with the following features: (1) The steric hindrance on the pyrazole rings L 3,3 ′ Me , L 5,5 ′ Me , L 5,3 ′ Me , L CF3 , and L Br was modified.(2) The steric hindrance was reduced on the peripheral thioether group: L SMe . (3) Finally, the presence of fluorine and bromine atoms in L CF3 and L Br offered the possibility to expand the type of interaction with respect to the ligands based on hydrocarbon substituents (CH 3 , phenyl, naphthyl). The effect of the anions was explored using different Ag(I) precursors such as AgPF 6 , AgBF 4 , AgCF 3 SO 3 , or AgNO 3 . A comparison of the crystal structures allowed for the tentative identification of the type of substituents able to induce the formation of CPs having permanent porosity to include a symmetric and moderate steric hindrance on the pyrazolyl moieties (four CH 3 ) and an aromatic and preorganized thioether moiety. An asymmetric steric hindrance on the pyrazole groups led to the formation of more varied structural types. Overall, the most frequently reported structural motifs are the porous hexameric systems and the molecular chains. ■ INTRODUCTIONOver the last three decades, the design of metal-based supramolecular assemblies has become one of the most intense research areas in chemistry and material science 1−7 due to the large number of potential applications of these materials, such as catalysis, 8,9 photochemistry, 10 luminescence, 11 sensing, 12 magnetism, 13,14 gas storage, 15−17 gas purification, 18,19 and medicine. 20 The ligand features and stereoelectronic characteristics of metal ions can control the arrangement of the supramolecular assemblies. The majority of transition metal ions usually exhibit a well-defined geometry (e.g., tetrahedral, square planar, or octahedral). In contrast, the geometry of d 10 metal centers is typically dictated by steric factors, ensuring a greater coordination flexibility. Additional control over the resulting structural arrangement can be achieved by the use of multitopic ligands, which can bridge different metal ions to build flexible network structures. The mutual orientation of the donor atoms defines the ligand geometry as well as the coordinative directionality; the orientation has a profound influence on the overall geometrical s...

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Section: Discussionmentioning

confidence: 99%

“…Depiction of the internal surface of the intracapsular (above) and intercapsular cavities of the [Ag 6 (L 3,5 ) 6 ](BF 4 ) 6 complex. 40,41 strength of the metal-anion interaction 73,74 or anion size 75 as key factors governing the overall architectures.…”

Section: ■ Conclusionmentioning

confidence: 99%

Silver(I) and Thioether-bis(pyrazolyl)methane Ligands: The Correlation between Ligand Functionalization and Coordination Polymer Architecture

Bassanetti

Atzeri

Tinonin

et al. 2016

Crystal Growth & Design

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An insight into the controllable synthesis of Cd(II) coordination polymers with packing-assistant luminescent property

et al. 2023

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Effect of noncovalent interactions on Ag(i)/Cu(ii) supramolecular architecture for dual-functional luminescence and semiconductive properties

Song

Fan

et al. 2016

CrystEngComm

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Four novel luminescent materials, namely, [Ag 3 (3,2′,3′-dpob)(bpy)] n (1•Ag), [Ag(3,3′,4′-H 2 dpob)(bpy)] n (2•Ag), [Ag 3 (3,2′,3′-Hdpob)(3,2′,3′-H 2 dpob)(bib) 3 •2H 2 O] n (3•Ag), and [Cu(3,2′,3′-Hdpob)(bib)•2H 2 O] n (4•Cu) [3,2′,3′-H 3 dpob = 3-(2′,3′-dicarboxylphenoxy)benzonic acid; 3,3′,4′-H 3 dpob = 3-(3′,4′-dicarboxylphenoxy)benzonic acid; bpy = 4,4′-bipyridine; bib = 1,4-bis(1-imidazoly)benzene] have been hydrothermally synthesized by mixed ligands and characterized using single crystal X-ray diffraction, infrared (IR), elemental analysis and thermogravimetric analysis (TGA). The crystal structures of four compounds indicate that the hydrogen bonding (O-H⋯O, C-H⋯O and C-H⋯π) and π⋯π stacking interactions play critical roles in the formation of the extended supramolecular array. 1•Ag displays a rare 3D compact structure with a 1D right-handed helical chain [-Ag1-CO2-Ag3-CO2-Ag1-]. 2•Ag and 3•Ag exhibit a 3D supramolecular architecture linked by intermolecular hydrogen bonds based on a 1D double-chain and 1D triple-chain, respectively. 4•Cu shows a 1D + 1D → 2D sheet, which is propagated to form an extended 3D structure with pcu (primitive cubic) topology via π⋯π stacking. The four compounds display remarkable narrow band emission with smaller full width at half-maximum (FWHM) (77

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Not Too Big and Not Too Small: “Goldilocks” Anion Size for Three-Dimensional Metal–Organic Frameworks Containing Oligothiophene Dinitrile Ligands (C₄H₂S)_n(CN)₂ (n = 1, 2, 3) Bridging Silver(I) Cations

Cited by 3 publications

References 55 publications

Silver(I) and Thioether-bis(pyrazolyl)methane Ligands: The Correlation between Ligand Functionalization and Coordination Polymer Architecture

Silver(I) and Thioether-bis(pyrazolyl)methane Ligands: The Correlation between Ligand Functionalization and Coordination Polymer Architecture

An insight into the controllable synthesis of Cd(II) coordination polymers with packing-assistant luminescent property

Effect of noncovalent interactions on Ag(i)/Cu(ii) supramolecular architecture for dual-functional luminescence and semiconductive properties

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