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Special Issue "Recent Developments in the Supramolecular Chemistry of Terpyridine–Metal Complexes"

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Macromolecular Chemistry".

Deadline for manuscript submissions: closed (31 December 2021) | Viewed by 2111

Special Issue Editors

Prof. Dr. Ulrich S. Schubert
grade E-Mail Website
Guest Editor
Laboratory of Organic and Macromolecular Chemistry (IOMC) Jena Center for Soft Matter (JCSM), Friedrich-Schiller-Universität Jena, Humboldtstr. 10, D-07743 Jena, Germany
Interests: automization; coordination chemistry; drug delivery; functional polymers; inkjet printing; metallo-supramolecular polymers; polymer batteries; polymer nanoparticles; self-healing materials
Special Issues, Collections and Topics in MDPI journals
Dr. Andreas Winter
E-Mail Website
Guest Editor
Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena, Humboldtstr. 10, 07743 Jena, Germany
Interests: metal complexes; metallo-supramolecular chemistry; opto-electronic devices; organic synthesis; photocatalysis
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

As the Guest Editors of Molecules` Special Issue on "Recent Developments in the Supramolecular Chemistry of Terpyridine–Metal Complexes”, it is our pleasure to invite you to submit an article on this topic. Terpyridine–metal complexes represent an important class of coordination compounds which are currently applied in a range of cutting-edge applications: (photo)catalysis, medicine, opto-electronics, photovoltaics, etc. Furthermore, such complexes have been implemented into polymer architectures, thus generating metallo-supramolecular polymers possessing self-assembly and stimuli-responsive properties (e.g., self-healing behavior). Finally, nano-sized architectures have been derived making use of metallo-supramolecular self-sorting/self-assembly processes. Many fascinating examples of shape-persistent or dynamic 2D/3D assemblies have been reported in recent years.

This Special Issue is devoted to the synthesis, characterization and/or application of new terpyridine–metal complexes. We are looking forward to receive contributions addressing either of these fields – on the small-molecule or macromolecular level. The article may be either a full paper or a communication based on your own current research in this area of coordination chemistry, or may be a focused review article on some aspect of the subject. All submissions will be subject to peer review.

Prof. Dr. Ulrich Schubert
Dr. Andreas Winter
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2300 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • biomedicine
  • catalysis
  • coordination polymers
  • energy storage
  • opto-electronics
  • nano materials
  • self-assembly
  • supramolecular polymers

Published Papers (2 papers)

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Research

Article
Adapting (4,4) Networks through Substituent Effects and Conformationally Flexible 3,2’:6’,3”-Terpyridines
Molecules 2021, 26(21), 6337; https://doi.org/10.3390/molecules26216337 - 20 Oct 2021
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Abstract
Coordination networks formed between Co(NCS)2 and 4’-substituted-[1,1’-biphenyl]-4-yl-3,2’:6’,3”-terpyridines in which the 4’-group is Me (1), H (2), F (3), Cl (4) or Br (5) are reported. [Co(1)2(NCS)2] [...] Read more.
Coordination networks formed between Co(NCS)2 and 4’-substituted-[1,1’-biphenyl]-4-yl-3,2’:6’,3”-terpyridines in which the 4’-group is Me (1), H (2), F (3), Cl (4) or Br (5) are reported. [Co(1)2(NCS)2]n·4.5nCHCl3, [Co(2)2(NCS)2]n·4.3nCHCl3, [Co(3)2(NCS)2]n·4nCHCl3, [Co(4)2(NCS)2]n, and [Co(5)2(NCS)2]n·nCHCl3 are 2D-networks directed by 4-connecting cobalt nodes. Changes in the conformation of the 3,2’:6’,3”-tpy unit coupled with the different peripheral substituents lead to three structure types. In [Co(1)2(NCS)2]n·4.5nCHCl3, [Co(2)2(NCS)2]n·4.3nCHCl3, [Co(3)2(NCS)2]n·4nCHCl3, cone-like arrangements of [1,1’-biphenyl]-4-yl units pack through pyridine…arene π-stacking, whereas Cl…π interactions are dominant in the packing in [Co(4)2(NCS)2]n. The introduction of the Br substituent in ligand 5 switches off both face-to-face π-stacking and halogen…π-interactions, and the packing interactions are more subtly controlled. Assemblies with organic linkers 13 are structurally similar and the lattice accommodates CHCl3 molecules in distinct cavities; thermogravimetric analysis confirmed that half the solvent in [Co(3)2(NCS)2]n·4nCHCl3 can be reversibly removed. Full article
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Article
Photoluminescence of Ni(II), Pd(II), and Pt(II) Complexes [M(Me2dpb)Cl] Obtained from C‒H Activation of 1,5-Di(2-pyridyl)-2,4-dimethylbenzene (Me2dpbH)
Molecules 2021, 26(16), 5051; https://doi.org/10.3390/molecules26165051 - 20 Aug 2021
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Abstract
The three complexes [M(Me2dpb)Cl] (M = Ni, Pd, Pt) containing the tridentate N,C,N-cyclometalating 3,5-dimethyl-1,5-dipyridyl-phenide ligand (Me2dpb) were synthesised using a base-assisted C‒H activation method. Oxidation potentials from cyclic voltammetry increased along the [...] Read more.
The three complexes [M(Me2dpb)Cl] (M = Ni, Pd, Pt) containing the tridentate N,C,N-cyclometalating 3,5-dimethyl-1,5-dipyridyl-phenide ligand (Me2dpb) were synthesised using a base-assisted C‒H activation method. Oxidation potentials from cyclic voltammetry increased along the series Pt < Ni < Pd from 0.15 to 0.74 V. DFT calculations confirmed the essentially ligand-centred π*-type character of the lowest unoccupied molecular orbital (LUMO) for all three complexes in agreement with the invariant reduction processes. For the highest occupied molecular orbitals (HOMO), contributions from metal dyz, phenyl C4, C2, C1, and C6, and Cl pz orbitals were found. As expected, the dz2 (HOMO-1 for Ni) is stabilised for the Pd and Pt derivatives, while the antibonding dx2−y2 orbital is de-stabilised for Pt and Pd compared with Ni. The long-wavelength UV-vis absorption band energies increase along the series Ni < Pt < Pd. The lowest-energy TD-DFT-calculated state for the Ni complex has a pronounced dz2-type contribution to the overall metal-to-ligand charge transfer (MLCT) character. For Pt and Pd, the dz2 orbital is energetically not available and a strongly mixed Cl-to-π*/phenyl-to-π*/M(dyz)-to-π* (XLCT/ILCT/MLCT) character is found. The complex [Pd(Me2dpb)Cl] showed a structured emission band in a frozen glassy matrix at 77 K, peaking at 468 nm with a quantum yield of almost unity as observed for the previously reported Pt derivative. No emission was observed from the Ni complex at 77 or 298 K. The TD-DFT-calculated states using the TPSSh functional were in excellent agreement with the observed absorption energies and also clearly assessed the nature of the so-called “dark”, i.e., d‒d*, excited configurations to lie low for the Ni complex (≥3.18 eV), promoting rapid radiationless relaxation. For the Pd(II) and Pt(II) derivatives, the “dark” states are markedly higher in energy with ≥4.41 eV (Pd) and ≥4.86 eV (Pt), which is in perfect agreement with the similar photophysical behaviour of the two complexes at low temperatures. Full article
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