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Molecules
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New Electro- and Photo-Functional Materials Based on Transition Metals
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New Electro- and Photo-Functional Materials Based on Transition Metals

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

Deadline for manuscript submissions: closed (28 February 2022) | Viewed by 9865

Special Issue Editors

Prof. Dr. Hiroshi Nishihara

E-Mail Website1 Website2
Guest Editor
Research Center for Science and Technology, Tokyo University of Science, Tokyo, Japan
Interests: coordination chemistry; electrochemistry; photochemistry; nanoscience
Prof. Dr. Hiroaki Maeda

E-Mail Website1 Website2
Guest Editor
Research Center for Science and Technology, Tokyo University of Science, Tokyo, Japan
Interests: coordination polymer; two-dimensional material; nano material; electrochemistry; coordination chemistry

Special Issue Information

Dear Colleagues,

The transition metal complex exhibits interesting redox, optical, magnetic, and chemical properties based on the d and f orbitals of the central metal. Therefore, it has been used not only for basic research to create new substances and to understand the correlation between their structures and properties, but also for present and future applications in the field of electronics, photonics, spintronics, and catalytic processes. Recently, evolutionary systems of these transition metal complexes have been developed. One such development is that transition metals are not the only protagonists and ligands also play the leading role. It is a new functional molecular system in which synergistic physical and chemical properties of metals and ligands appear by introducing redox activity, photo-responsivity, and magnetism into ligands. The other is a system in which transition metal complex units are connected to form one-dimensional, two-dimensional, and three-dimensional polymeric structures. New properties can emerge from the physicochemical interaction between the units. When the inner space of the molecular frameworks can contain guest molecules, the host–guest interaction is expected to originate novel functionality. This Special Issue invites papers on new electro-, photo-, and magneto-functional materials based on transition metal complexes.

Prof. Dr. Hiroshi Nishihara
Prof. Dr. Hiroaki Maeda
Guest Editors

Manuscript Submission Information

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Keywords

  • Redox 
  • Luminescence 
  • Chromism

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Published Papers (3 papers)

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Research

10 pages, 2186 KiB  
Article
Synthesis, Structure, and Photophysical Properties of Yellow-Green and Blue Photoluminescent Dinuclear and Octanuclear Copper(I) Iodide Complexes with a Disilanylene-Bridged Bispyridine Ligand
by Toyotaka Nakae, Hiroto Miyabe, Masaki Nishio, Teppei Yamada and Yoshinori Yamanoi
Molecules 2021, 26(22), 6852; https://doi.org/10.3390/molecules26226852 - 13 Nov 2021
Cited by 6 | Viewed by 3171
Abstract
The synthesis, structural, and photophysical investigations of CuI complexes with a disilanylene-bridged bispyridine ligand 1 are herein presented. Dinuclear (2) and ladder-like (3) octanuclear copper(I) complexes were straightforwardly prepared by exactly controlling the ratio of CuI/ligand 1. Single-crystal [...] Read more.
The synthesis, structural, and photophysical investigations of CuI complexes with a disilanylene-bridged bispyridine ligand 1 are herein presented. Dinuclear (2) and ladder-like (3) octanuclear copper(I) complexes were straightforwardly prepared by exactly controlling the ratio of CuI/ligand 1. Single-crystal X-ray analysis confirmed that dinuclear complex 2 had no apparent π…π stacking whereas octanuclear complex 3 had π…π stacking in the crystal packing. In the solid state, the complexes display yellow-green (λem = 519 nm, Φ = 0.60, τ = 11 µs, 2) and blue (λem = 478 nm, Φ = 0.04, τ = 2.6 µs, 3) phosphorescence, respectively. The density functional theory calculations validate the differences in their optical properties. The difference in the luminescence efficiency between 2 and 3 is attributed to the presence of π…π stacking and the different luminescence processes. Full article
(This article belongs to the Special Issue New Electro- and Photo-Functional Materials Based on Transition Metals)
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15 pages, 4468 KiB  
Article
Solid-State Structures and Photoluminescence of Lamellar Architectures of Cu(I) and Ag(I) Paddlewheel Clusters with Hydrogen-Bonded Polar Guests
by Haruki Inoue, Yuga Yamashita, Yoshiki Ozawa, Toshikazu Ono and Masaaki Abe
Molecules 2021, 26(21), 6731; https://doi.org/10.3390/molecules26216731 - 6 Nov 2021
Cited by 2 | Viewed by 2762
Abstract
Two hexanuclear paddlewheel-like clusters appending six carboxylic-acid pendants have been isolated with the inclusion of polar solvent guests: [Cu6(Hmna)6]·7DMF (1·7DMF) and [Ag6(Hmna)6]·8DMSO (2·8DMSO), where H2mna = 2-mercaptonicotininc acid, DMF [...] Read more.
Two hexanuclear paddlewheel-like clusters appending six carboxylic-acid pendants have been isolated with the inclusion of polar solvent guests: [Cu6(Hmna)6]·7DMF (1·7DMF) and [Ag6(Hmna)6]·8DMSO (2·8DMSO), where H2mna = 2-mercaptonicotininc acid, DMF = N,N’-dimethylformamide, and DMSO = dimethyl sulfoxide. The solvated clusters, together with their fully desolvated forms 1 and 2, have been characterized by FTIR, UV–Vis diffuse reflectance spectroscopy, TG-DTA analysis, and DFT calculations. Crystal structures of two solvated clusters 1·7DMF and 2·8DMSO have been unambiguously determined by single-crystal X-ray diffraction analysis. Six carboxylic groups appended on the clusters trap solvent guests, DMF or DMSO, through H-bonds. As a result, alternately stacked lamellar architectures comprising of a paddlewheel cluster layer and H-bonded solvent layer are formed. Upon UV illumination (λex = 365 nm), the solvated hexasilver(I) cluster 2·8DMSO gives intense greenish-yellow photoluminescence in the solid state (λPL = 545 nm, ΦPL = 0.17 at 298 K), whereas the solvated hexacopper(I) cluster 1·7DMF displays PL in the near-IR region (λPL = 765 nm, ΦPL = 0.38 at 298 K). Upon complete desolvation, a substantial bleach in the PL intensity (ΦPL < 0.01) is observed. The desorption–sorption response was studied by the solid-state PL spectroscopy. Non-covalent interactions in the crystal including intermolecular H-bonds, CH⋯π interactions, and π⋯π stack were found to play decisive roles in the creation of the lamellar architectures, small-molecule trap-and-release behavior, and guest-induced luminescence enhancement. Full article
(This article belongs to the Special Issue New Electro- and Photo-Functional Materials Based on Transition Metals)
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Figure 1

11 pages, 4916 KiB  
Article
Ultralong π-Conjugated Bis(terpyridine)metal Polymer Wires Covalently Bound to a Carbon Electrode: Fast Redox Conduction and Redox Diode Characteristics
by Kuo-Hui Wu, Ryota Sakamoto, Hiroaki Maeda, Eunice Jia Han Phua and Hiroshi Nishihara
Molecules 2021, 26(14), 4267; https://doi.org/10.3390/molecules26144267 - 14 Jul 2021
Cited by 5 | Viewed by 2830
Abstract
We developed an efficient and convenient electrochemical method to synthesize π-conjugated redox metal-complex linear polymer wires composed of azobenzene-bridged bis(terpyridine)metal (2-M, M = Fe, Ru) units covalently immobilized on glassy carbon (GC). Polymerization proceeds by electrochemical oxidation of bis(4′-(4-anilino)-2,2′:6′,2″-terpyridine)metal (1-M [...] Read more.
We developed an efficient and convenient electrochemical method to synthesize π-conjugated redox metal-complex linear polymer wires composed of azobenzene-bridged bis(terpyridine)metal (2-M, M = Fe, Ru) units covalently immobilized on glassy carbon (GC). Polymerization proceeds by electrochemical oxidation of bis(4′-(4-anilino)-2,2′:6′,2″-terpyridine)metal (1-M) in a water–acetonitrile–HClO4 solution, affording ultralong wires up to 7400 mers (corresponding to ca. 15 μm). Both 2-Fe and 2-Ru undergo reversible redox reactions, and their redox behaviors indicate remarkably fast redox conduction. Anisotropic hetero-metal-complex polymer wires with Fe and Ru centers are constructed via stepwise electropolymerization. The cyclic voltammograms of two hetero-metal-complex polymer wires, GC/[2-Fe]–[2-Ru] (3) and GC/[2-Ru]–[2-Fe] (4), show irreversible redox reactions with opposite electron transfer characteristics, indicating redox diodelike behavior. In short, the present electrochemical method is useful to synthesize polymer wire arrays and to integrate functional molecules on carbon. Full article
(This article belongs to the Special Issue New Electro- and Photo-Functional Materials Based on Transition Metals)
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