Special Issue "Organometallic Macrocycles and Their Applications"

A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Organometallic Chemistry".

Deadline for manuscript submissions: closed (30 June 2018)

Special Issue Editor

Guest Editor
Professor Rainer Winter

Universitat Konstanz, Department of Chemistry, Konstanz, Germany
Website | E-Mail
Interests: organometallic chemistry; spectroelectrochemistry; mixed-valent compounds; valence tautomerism; electrochromic compounds; metallamacrocyclic complexes; molecule-based conductive materials; dual emitters

Special Issue Information

Dear Colleagues,

Apart from their inherent beauty, cyclic structures can exhibit properties and functions that surpass those of linear architectures constructed from the same constituents. Macrocycles incorporating transition metal-coligand entities as integral building blocks offer particularly fascinating prospects. This is due to their structure-directing abilities, as well as the preferred coordination numbers and coordination geometries. The field of metallamacrocyclic complexes has, meanwhile, matured beyond the directed synthesis and characterization of such architectures to explore and exploit their physical properties. Examples are electron transfer from the coordination centers or the bridging ligands or optical charge transfer between these constituents with forays into the field of molecule-based electronics. Other work employs the sizable interior cavities for selective host–guest chemistry with emerging applications as structurally adaptive and stimuli-responsive materials or in catalysis, biology and medicine. This Special Issue of Inorganics highlights the many facets of metallamacrocyclic chemistry.

Prof. Dr. Rainer Winter
Guest Editor

Manuscript Submission Information

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Keywords

  • cage compounds
  • metallacycles
  • host–guest chemistry
  • stimuli-responsive materials
  • self-assembly
  • charge transfer
  • energy transfer

Published Papers (2 papers)

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Research

Open AccessArticle Metallated [3]Ferrocenophanes Containing P3M Bridges (M = Li, Na, K) §
Received: 19 June 2018 / Revised: 4 July 2018 / Accepted: 6 July 2018 / Published: 11 July 2018
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Abstract
Alkali-metal phosphanides can be embedded into a [3]ferrocenophane scaffold giving rise to bicyclic ferrocenophanes [MFe(C5H4PtBu)2P] (M = Li, Na, K). Coordination of the alkali-metal ions takes place via the terminal phosphorus atoms adopting a puckered
[...] Read more.
Alkali-metal phosphanides can be embedded into a [3]ferrocenophane scaffold giving rise to bicyclic ferrocenophanes [MFe(C5H4PtBu)2P] (M = Li, Na, K). Coordination of the alkali-metal ions takes place via the terminal phosphorus atoms adopting a puckered P3M four-membered ring. All compounds were characterized via single-crystal X-ray diffraction and multinuclear NMR spectroscopy (1H, 31P, 7Li), whereas 13C NMR data could only be recorded for the Li derivative, owing to the limited solubility of its heavier congeners in unreactive solvents. Full article
(This article belongs to the Special Issue Organometallic Macrocycles and Their Applications)
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Open AccessCommunication Synthesis, Structural, and Magnetic Characterization of a Mixed 3d/4f 12-Metallacrown-4 Family of Complexes
Received: 21 June 2018 / Revised: 2 July 2018 / Accepted: 5 July 2018 / Published: 7 July 2018
PDF Full-text (1257 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
A new family of complexes (tBu4N){[LnIII(O2CBut)4][12-MC-Mn(III)N(shi)-4]}·5CH2Cl2 (Ln = Gd (1) and Tb (2)), (tBu4N)2{[YIII(O
[...] Read more.
A new family of complexes (tBu4N){[LnIII(O2CBut)4][12-MC-Mn(III)N(shi)-4]}·5CH2Cl2 (Ln = Gd (1) and Tb (2)), (tBu4N)2{[YIII(O2CBut)4][12-MC-Mn(III)N(shi)-4]}(ClO4) (3); where shiH3 = salicylhydroxamic acid; ButCO2 = pivalate ions; tBu4N = tetrabutylammonium and ClO4 = perchlorate ions, has been isolated. The reaction of salicylhydroxamic acid with Mn(O2CBut)2·2H2O, Ln(NO3)3·xH2O, tBu4NClO4 in the presence of morpholine (C4H9NO) led to the isolation of compounds 13. The complexes belong to the 12-MC-4 family of Metallacrowns (MCs) possessing a central {Mn4IIILnIII(µ-NO)4}11+ core with the four MnIII atoms occupying the periphery positions, while the formed [Mn–N–O] repeating unit, assists in the accommodation of the LnIII atom in the center of the ring. Peripheral ligation is provided by four η11:μ pivalate ions. Direct current magnetic susceptibility (dc) measurements revealed the presence of predominant antiferromagnetic exchange interactions within the metal centers. A 1-J fitting model was used in order to quantify the MnIII–MnIII interactions and fitting of the data, for the diamagnetic YIII analogue, gave J = −3.74 cm−1 and gMn(III) = 2.07. Fitting of the {Mn4Gd} compound using a 2-J model, counting additionally for the MnIII–GdIII interactions, revealed values of J1 = −3.52 cm−1, J2 = −0.45 cm−1, and gMn(III) = 1.99. Full article
(This article belongs to the Special Issue Organometallic Macrocycles and Their Applications)
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