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Inorganics
Special Issues
Organometallic Macrocycles and Their Applications
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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) | Viewed by 19939

Special Issue Editor

Prof. Dr. Rainer Winter

E-Mail Website
Guest Editor
Department of Chemistry, Universitat Konstanz, 78464 Konstanz, Germany
Interests: organometallic chemistry; ruthenium complexes; (spectro)electrochemistry; metallocenes; valence tautomerism; mixed-valent chemistry; luminescent platinum complexes; metallamacrocyclic complexes
Special Issues, Collections and Topics in MDPI journals

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

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Keywords

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

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Published Papers (5 papers)

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Research

16 pages, 2848 KiB  
Article
Arene Ruthenium Metalla-Assemblies with Anthracene Moieties for PDT Applications
by Marie Gaschard, Farzaneh Nehzat, Thomas Cheminel and Bruno Therrien
Inorganics 2018, 6(3), 97; https://doi.org/10.3390/inorganics6030097 - 12 Sep 2018
Cited by 16 | Viewed by 4617
Abstract
The synthesis and characterization of three metalla-rectangles of the general formula [Ru4(η6-p-cymene)4(μ4-clip)2(μ2-Lanthr)2][CF3SO3]4 (Lanthr: 9,10-bis(3,3’-ethynylpyridyl) anthracene; clip [...] Read more.
The synthesis and characterization of three metalla-rectangles of the general formula [Ru4(η6-p-cymene)4(μ4-clip)2(μ2-Lanthr)2][CF3SO3]4 (Lanthr: 9,10-bis(3,3’-ethynylpyridyl) anthracene; clip = oxa: oxalato; dobq: 2,5-dioxido-1,4-benzoquinonato; donq: 5,8-dioxido-1,4-naphthoquinonato) are presented. The molecular structure of the metalla-rectangle [Ru4(η6-p-cymene)4(μ4-oxa)2(μ2-Lanthr)2]4+ has been confirmed by the single-crystal X-ray structure analysis of [Ru4(η6-p-cymene)4(μ4-oxa)2(μ2-Lanthr)2][CF3SO3]4 · 4 acetone (A2 · 4 acetone), thus showing the anthracene moieties to be available for reaction with oxygen. While the formation of the endoperoxide form of Lanthr was observed in solution upon white light irradiation, the same reaction does not occur when Lanthr is part of the metalla-assemblies. Full article
(This article belongs to the Special Issue Organometallic Macrocycles and Their Applications)
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8 pages, 1142 KiB  
Article
Synthesis and Characterisation of Linear and Towards Cyclic Diferrocenes with Alkynyl Spacers
by Lucy E. Wilson, Xueying Jian, Andrew J. P. White and Nicholas J. Long
Inorganics 2018, 6(3), 95; https://doi.org/10.3390/inorganics6030095 - 11 Sep 2018
Cited by 3 | Viewed by 3424
Abstract
Ferrocenediyl systems offer a motif that incorporates multiple functionality and redox-active centers, enabling these units to be used as molecular scaffolds in linear and cyclic compounds. Herein, we discuss a new modular methodology for the synthesis and incorporation of ferrocenediyl motifs within extended [...] Read more.
Ferrocenediyl systems offer a motif that incorporates multiple functionality and redox-active centers, enabling these units to be used as molecular scaffolds in linear and cyclic compounds. Herein, we discuss a new modular methodology for the synthesis and incorporation of ferrocenediyl motifs within extended conjugated systems. We have synthesized a family of compounds featuring ferrocenediyl-ethynyl units with various para-substituted aromatic linkages. Extended linear, open-chain species have been isolated and understanding towards the analogous cyclic compounds gained. The new compounds have been probed using NMR, mass spectrometry, cyclic voltammetry and X-ray crystallography to gain further understanding of their structural and electronic properties. Full article
(This article belongs to the Special Issue Organometallic Macrocycles and Their Applications)
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21 pages, 5186 KiB  
Article
Tetraruthenium Metallamacrocycles with Potentially Coordinating Appended Functionalities
by Patrick Anders, Mario Robin Rapp, Michael Linseis and Rainer F. Winter
Inorganics 2018, 6(3), 73; https://doi.org/10.3390/inorganics6030073 - 24 Jul 2018
Cited by 10 | Viewed by 4146
Abstract
We present four new tetraruthenium macrocycles built from two 1,4-divinylphenylene diruthenium and two isophthalic acid building blocks with peripheral, potentially mono- or tridentate donor functions attached to the isophthalic linkers. These macrocycles are characterized by multinuclear NMR spectroscopy, mass spectrometry and, in the [...] Read more.
We present four new tetraruthenium macrocycles built from two 1,4-divinylphenylene diruthenium and two isophthalic acid building blocks with peripheral, potentially mono- or tridentate donor functions attached to the isophthalic linkers. These macrocycles are characterized by multinuclear NMR spectroscopy, mass spectrometry and, in the case of the thioacetyl-appended complex 4, by X-ray crystallography. Cyclic and square wave voltammetry establish that the macrocycles can be oxidized in four consecutive redox steps that come as two pairs of two closely spaced one-electron waves. Spectroscopic changes observed during IR and UV/Vis/NIR spectroelectrochemical experiments (NIR = near infrared) show that the isophthalate linkers insulate the electroactive divinylphenylene diruthenium moieties against each other. The macrocycles exhibit nevertheless pronounced polyelectrochromism with highly intense absorptions in the Vis (2+/4+ states) and the NIR (2+ states) with extinction coefficients of up to >100,000 M−1·cm−1. The strong absorptivity enhancement with respect to the individual divinylphenylene diruthenium building blocks is attributed to conformational restrictions imposed by the macrocycle backbone. Moreover, the di- and tetracations of these macrocycles are paramagnetic as revealed by EPR spectroscopy. Full article
(This article belongs to the Special Issue Organometallic Macrocycles and Their Applications)
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9 pages, 2021 KiB  
Article
Metallated [3]Ferrocenophanes Containing P3M Bridges (M = Li, Na, K) §
by Stefan Isenberg, Lisa-Marie Frenzel, Clemens Bruhn and Rudolf Pietschnig
Inorganics 2018, 6(3), 67; https://doi.org/10.3390/inorganics6030067 - 11 Jul 2018
Cited by 8 | Viewed by 3451
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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11 pages, 1257 KiB  
Communication
Synthesis, Structural, and Magnetic Characterization of a Mixed 3d/4f 12-Metallacrown-4 Family of Complexes
by Angeliki A. Athanasopoulou, Luca M. Carrella and Eva Rentschler
Inorganics 2018, 6(3), 66; https://doi.org/10.3390/inorganics6030066 - 7 Jul 2018
Cited by 9 | Viewed by 3733
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 1–3. 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 η1:η1: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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