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Coordination Programming for Electro-, Magneto-, and Photofunctional Molecular Systems: A Theme Issue in Honor of Prof. Dr. Hiroshi Nishihara

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

Deadline for manuscript submissions: closed (31 December 2021) | Viewed by 23268

Special Issue Editors

Dr. Ryota Sakamoto

E-Mail Website
Guest Editor
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan
Interests: coordination chemistry; nanoscience; molecular low-dimensional systems; coordination polymers
Prof. Dr. Wai-Yeung Wong (Raymond)

grade E-Mail Website
Guest Editor
Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Hong Kong, China
Interests: inorganic chemistry; organometallic chemistry; materials chemistry; metallopolymers; metallophosphors
Dr. Qian Liu

E-Mail Website
Assistant Guest Editor
School of Chemical and Environmental Engineering, Anhui Polytechnic University, Wuhu 241000, Anhui, China
Interests: organometallic chemistry; coordination chemistry; MOF nanosheets; optoelectronic functional materials; energy storage materials

Special Issue Information

Dear Colleagues,

Professor Hiroshi Nishihara received his B. Sc. degree in 1977, M. Sc. in 1979, and D. Sc. in 1982, from The University of Tokyo. He was appointed research associate of Department of Chemistry at Keio University in 1982, and he was promoted Lecturer in 1990, and Associate Professor in 1992. From 1996 to 2020, he was a Professor of Department of Chemistry, School of Science at The University of Tokyo. In 2020, He moved to Research Institute for Science and Technology, Tokyo University of Science. He also worked as a visiting research associate of Department of Chemistry at The University of North Carolina at Chapel Hill (1987-1989), and as a researcher of PRESTO, JST (1992-1996). He received Docteur Honoris Causa from University of Bordeaux in 2011, Commendation for Science and Technology by MEXT in 2014, and The Chemical Society of Japan Award in 2015. Professor Hiroshi Nishihara held important scientific society posts successively, such as the Dean of The Electochemical Society of Japan, the Dean of Japan Society of Coordination Chemistry, and the Vice President of The Chemical Society of Japan.

Professor Hiroshi Nishihara has established a concept of “Coordination Programming”. Taking advantage of coordination chemistry, or precise and flexible arrangement and bonding of ligand molecules and metal atoms or ions, a series of elaborate molecular superstructures has been realized, including molecular low-dimensional systems (coordination nanowires and nanosheets). Moreover, he has demonstrated that the rich and unique functions of the metal complexes motifs incorporated in the molecular superstructures allow the latter to behave as intelligent molecular systems that feature hierarchical multifunctions, leading to future nanomaterials such as molecular scale electronics.

It is with this in mind that we honor him on the occasion of his retirement from the University of Tokyo for his outstanding achievements in the areas of coordination chemistry, nanoscience, and electrochemistry, as well as his critical role in advancing the field. He remains an inspiration to all, and we are pleased to invite you to submit a publication for this Special Issue.

Dr. Ryota Sakamoto
Prof. Dr. Wai-Yeung Wong (Raymond)
Guest Editors

Dr. Qian Liu
Assistant Guest Editor

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 2700 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

  • nanosheets
  • nanowires
  • nanoparticles
  • coordination compounds
  • polynuculear metal complexes
  • metal cluster complexes
  • molecular electronics
  • nanomaterials

Published Papers (9 papers)

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Research

11 pages, 3058 KiB  
Article
Ferrocene-Containing Pseudorotaxanes in Crystals: Aromatic Interactions with Hammett Correlation
by Yuji Suzaki, Tomoko Abe, Asami Takei, Yugo Fukuchi, Take-aki Koizumi, Kohtaro Osakada and Masaki Horie
Molecules 2022, 27(5), 1745; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules27051745 - 07 Mar 2022
Viewed by 2049
Abstract
Single crystals of pseudorotaxanes, [(FcCH2NH2CH2Ar)(DB24C8)][PF6] (DB24C8 = dibenzo[24]crown-8, Fc = Fe(C5H4)(C5H5), Ar = -C6H3-3,4-Cl2, -C6H3-3,4-F2, [...] Read more.
Single crystals of pseudorotaxanes, [(FcCH2NH2CH2Ar)(DB24C8)][PF6] (DB24C8 = dibenzo[24]crown-8, Fc = Fe(C5H4)(C5H5), Ar = -C6H3-3,4-Cl2, -C6H3-3,4-F2, -C6H4-4-F, -C6H4-4-Cl, -C6H4-4-Br, -C6H3-3-F-4-Me, -C6H4-4-I) and [(FcCH2NH2CH2C6H4-4-Me)(DB24C8)][Ni(dmit)2] (dmit = 1,3-dithiole-2,4,5-dithiolate), were obtained from solutions containing DB24C8 and ferrocenylmethyl(arylmethyl)ammonium. X-ray crystallographic analyses of the pseudorotaxanes revealed that the aryl ring of the axle moiety and the catechol ring of the macrocyclic component were at close centroid distances and parallel or tilted orientation. The structures with parallel aromatic rings showed correlation of the distances between the centroids to Hammett substituent constants of the aryl groups. Full article
(This article belongs to the Special Issue Coordination Programming for Electro-, Magneto-, and Photofunctional Molecular Systems: A Theme Issue in Honor of Prof. Dr. Hiroshi Nishihara)
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13 pages, 1769 KiB  
Article
Theoretical Study on Redox Potential Control of Iron-Sulfur Cluster by Hydrogen Bonds: A Possibility of Redox Potential Programming
by Iori Era, Yasutaka Kitagawa, Natsumi Yasuda, Taigo Kamimura, Naoka Amamizu, Hiromasa Sato, Keigo Cho, Mitsutaka Okumura and Masayoshi Nakano
Molecules 2021, 26(20), 6129; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26206129 - 11 Oct 2021
Cited by 6 | Viewed by 2291
Abstract
The effect of hydrogen bonds around the active site of Anabaena [2Fe-2S] ferredoxin (Fd) on a vertical ionization potential of the reduced state (IP(red)) is examined based on the density functional theory (DFT) calculations. The results indicate that a single hydrogen [...] Read more.
The effect of hydrogen bonds around the active site of Anabaena [2Fe-2S] ferredoxin (Fd) on a vertical ionization potential of the reduced state (IP(red)) is examined based on the density functional theory (DFT) calculations. The results indicate that a single hydrogen bond increases the relative stability of the reduced state, and shifts IP(red) to a reductive side by 0.31–0.33 eV, regardless of the attached sulfur atoms. In addition, the IP(red) value can be changed by the number of hydrogen bonds around the active site. The results also suggest that the redox potential of [2Fe-2S] Fd is controlled by the number of hydrogen bonds because IP(red) is considered to be a major factor in the redox potential. Furthermore, there is a possibility that the redox potentials of artificial iron-sulfur clusters can be finely controlled by the number of the hydrogen bonds attached to the sulfur atoms of the cluster. Full article
(This article belongs to the Special Issue Coordination Programming for Electro-, Magneto-, and Photofunctional Molecular Systems: A Theme Issue in Honor of Prof. Dr. Hiroshi Nishihara)
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8 pages, 1098 KiB  
Article
Structural and Magnetic Studies on Nickel(II) and Cobalt(II) Complexes with Polychlorinated Diphenyl(4-pyridyl)methyl Radical Ligands
by Ryota Matsuoka, Tatsuhiro Yoshimoto, Yasutaka Kitagawa and Tetsuro Kusamoto
Molecules 2021, 26(18), 5596; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26185596 - 15 Sep 2021
Cited by 5 | Viewed by 2269
Abstract
New magnetic metal complexes with organic radical ligands, [M(hfac)2(PyBTM)2] (M = NiII, CoII; hfac = hexafluoroacetylacetonato, PyBTM = (3,5-dichloro-4-pyridyl)bis(2,4,6-trichlorophenyl)methyl radical), were prepared and their crystal structures, magnetic properties, and electronic structures were investigated. Metal ions [...] Read more.
New magnetic metal complexes with organic radical ligands, [M(hfac)2(PyBTM)2] (M = NiII, CoII; hfac = hexafluoroacetylacetonato, PyBTM = (3,5-dichloro-4-pyridyl)bis(2,4,6-trichlorophenyl)methyl radical), were prepared and their crystal structures, magnetic properties, and electronic structures were investigated. Metal ions in [M(hfac)2(PyBTM)2] constructed distorted octahedral coordination geometry, where the two PyBTM molecules ligated in the trans configuration. Magnetic investigation using a SQUID magnetometer revealed that χT increased with decreasing temperature from 300 K in the two complexes, indicating an efficient intramolecular ferromagnetic exchange interaction taking place between the spins on PyBTM and M with J/kB of 21.8 K and 11.8 K for [NiII(hfac)2(PyBTM)2] and [CoII(hfac)2(PyBTM)2]. The intramolecular ferromagnetic couplings in the two complexes could be explained by density functional theory calculations, and would be attributed to a nearly orthogonal relationship between the spin orbitals on PyBTM and the metal ions. These results demonstrate that pyridyl-containing triarylmethyl radicals are key building blocks for magnetic molecular materials with controllable/predictable magnetic interactions. Full article
(This article belongs to the Special Issue Coordination Programming for Electro-, Magneto-, and Photofunctional Molecular Systems: A Theme Issue in Honor of Prof. Dr. Hiroshi Nishihara)
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11 pages, 1761 KiB  
Article
Sensing Properties of NH2-MIL-101 Series for Specific Amino Acids via Turn-On Fluorescence
by Jing Dong, Xiao-Yao Dao, Xiao-Yu Zhang, Xiu-Du Zhang and Wei-Yin Sun
Molecules 2021, 26(17), 5336; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26175336 - 02 Sep 2021
Cited by 15 | Viewed by 3014
Abstract
Metal–organic frameworks (MOFs) have been demonstrated to be desired candidates for sensing definite species owing to their tunable composition, framework structure and functionality. In this work, the NH2-MIL-101 series was utilized for sensing specific amino acids. The results show that cysteine [...] Read more.
Metal–organic frameworks (MOFs) have been demonstrated to be desired candidates for sensing definite species owing to their tunable composition, framework structure and functionality. In this work, the NH2-MIL-101 series was utilized for sensing specific amino acids. The results show that cysteine (Cys) can significantly enhance the fluorescence emission of NH2-MIL-101-Fe suspended in water, while NH2-MIL-101-Al exhibits the ability to sense lysine (Lys), arginine (Arg) and histidine (His) in aqueous media via turn-on fluorescence emission. Titration experiments ensure that NH2-MIL-101-Fe and NH2-MIL-101-Al can selectively and quantitatively detect these amino acids. The sensing mechanism was examined and discussed. The results of this study show that the metal centers in MOFs are crucial for sensing specific amino acids. Full article
(This article belongs to the Special Issue Coordination Programming for Electro-, Magneto-, and Photofunctional Molecular Systems: A Theme Issue in Honor of Prof. Dr. Hiroshi Nishihara)
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12 pages, 1689 KiB  
Article
Development of Highly Sensitive Raman Spectroscopy for Subnano and Single-Atom Detection
by Yuansen Tang, Naoki Haruta, Akiyoshi Kuzume and Kimihisa Yamamoto
Molecules 2021, 26(16), 5099; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26165099 - 23 Aug 2021
Cited by 2 | Viewed by 2873
Abstract
Direct detection and characterisation of small materials are fundamental challenges in analytical chemistry. A particle composed of dozens of metallic atoms, a so-called subnano-particle (SNP), and a single-atom catalyst (SAC) are ultimate analysis targets in terms of size, and the topic is now [...] Read more.
Direct detection and characterisation of small materials are fundamental challenges in analytical chemistry. A particle composed of dozens of metallic atoms, a so-called subnano-particle (SNP), and a single-atom catalyst (SAC) are ultimate analysis targets in terms of size, and the topic is now attracting increasing attention as innovative frontier materials in catalysis science. However, characterisation techniques for the SNP and SAC adsorbed on substrates requires sophisticated and large-scale analytical facilities. Here we demonstrate the development of an ultrasensitive, laboratory-scale, vibrational spectroscopic technique to characterise SNPs and SACs. The fine design of nano-spatial local enhancement fields generated by the introduction of anisotropic stellate-shaped signal amplifiers expands the accessibility of small targets on substrates into evanescent electromagnetic fields, achieving not only the detection of isolated small targets but also revealing the effects of intermolecular/interatomic interactions within the subnano configuration under actual experimental conditions. Such a development of “in situ subnano spectroscopy” will facilitate a comprehensive understanding of subnano and SAC science. Full article
(This article belongs to the Special Issue Coordination Programming for Electro-, Magneto-, and Photofunctional Molecular Systems: A Theme Issue in Honor of Prof. Dr. Hiroshi Nishihara)
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12 pages, 3105 KiB  
Article
Synthesis of Bis-Terpyridine-Based Metallopolymers and the Thermoelectric Properties of Their Single Walled Carbon Nanotube Composites
by Jiahua Li, Zeling Guo, Linli Xu and Wai-Yeung Wong
Molecules 2021, 26(9), 2560; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26092560 - 28 Apr 2021
Cited by 3 | Viewed by 2026
Abstract
Although the organic and the conventional inorganic thermoelectric (TE) materials have been extensively developed in recent years, the number of cases involving conducting metallopolymers is still quite limited. In view of the versatile coordination capability of the terpyridine fraction and the electron-rich nature [...] Read more.
Although the organic and the conventional inorganic thermoelectric (TE) materials have been extensively developed in recent years, the number of cases involving conducting metallopolymers is still quite limited. In view of the versatile coordination capability of the terpyridine fraction and the electron-rich nature of the 3,4-ethylenedioxythiophene moiety, a bis-terpyridine-featured ligand was designed, and a series of metallopolymers were then synthesized. Upon the addition of single-walled carbon nanotube (SWCNT), the TE properties of the resulting metallopolymer-SWCNT composite films were investigated. It was found that metal centres played an important role in affecting the morphology of the thin films, which was a key factor that determined the TE performances of the composites. Additionally, the energy levels of the metallopolymers were feasibly tuned by selecting different metal centres. With the combined effects of a uniform and condensed surface and an optimized band structure, the highest power factor was achieved by the Cu(II)-containing metallopolymer-SWCNT composite at the doping ratio of 75%, which reached 38.3 μW·m−1·K−2. Full article
(This article belongs to the Special Issue Coordination Programming for Electro-, Magneto-, and Photofunctional Molecular Systems: A Theme Issue in Honor of Prof. Dr. Hiroshi Nishihara)
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15 pages, 5188 KiB  
Article
The TDDFT Excitation Energies of the BODIPYs; The DFT and TDDFT Challenge Continues
by Adrien Schlachter, Alexandre Fleury, Kevin Tanner, Armand Soldera, Benoit Habermeyer, Roger Guilard and Pierre D. Harvey
Molecules 2021, 26(6), 1780; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26061780 - 22 Mar 2021
Cited by 12 | Viewed by 3256
Abstract
The derivatives of 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) are pivotal ingredients for a large number of functional, stimuli-responsive materials and therapeutic molecules based on their photophysical properties, and there is a urgent need to understand and predict their optical traits prior to investing a large amount [...] Read more.
The derivatives of 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) are pivotal ingredients for a large number of functional, stimuli-responsive materials and therapeutic molecules based on their photophysical properties, and there is a urgent need to understand and predict their optical traits prior to investing a large amount of resources in preparing them. Density functional theory (DFT) and time-dependent DFT (TDDFT) computations were performed to calculate the excitation energies of the lowest-energy singlet excited state of a large series of common BODIPY derivatives employing various functional aiming at the best possible combination providing the least deviations from the experimental values. Using the common “fudge” correction, a series of combinations was investigated, and a methodology is proposed offering equal or better performances than what is reported in the literature. Full article
(This article belongs to the Special Issue Coordination Programming for Electro-, Magneto-, and Photofunctional Molecular Systems: A Theme Issue in Honor of Prof. Dr. Hiroshi Nishihara)
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8 pages, 1264 KiB  
Article
Synthesis of Bis{meso-Tetrakis(4-N-alkylpyridiniumyl)porphyrinato}cerium and Its Redox Switching Behavior
by Toshio Nishino, Yasuyuki Yamada, Ayumi Yamamoto and Kentaro Tanaka
Molecules 2021, 26(4), 790; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26040790 - 03 Feb 2021
Cited by 1 | Viewed by 2141
Abstract
A novel double-decker porphyrin complex, bis{meso-tetrakis(4-N-alkylpyridiniumyl)porphyrinato}cerium, was prepared. Electrochemical measurements revealed that this complex exhibited reversible redox waves corresponding to a 1e– redox reaction of the cerium center. Treating the complex alternately with an oxidant and a reductant [...] Read more.
A novel double-decker porphyrin complex, bis{meso-tetrakis(4-N-alkylpyridiniumyl)porphyrinato}cerium, was prepared. Electrochemical measurements revealed that this complex exhibited reversible redox waves corresponding to a 1e– redox reaction of the cerium center. Treating the complex alternately with an oxidant and a reductant resulted in the reversible redox switching between the oxidized and reduced states in an organic solvent. Full article
(This article belongs to the Special Issue Coordination Programming for Electro-, Magneto-, and Photofunctional Molecular Systems: A Theme Issue in Honor of Prof. Dr. Hiroshi Nishihara)
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9 pages, 2350 KiB  
Communication
Synthesis of an Alternated Heterobimetallic Supramolecular Polymer Based on Ru(II) and Fe(II)
by Manas Kumar Bera, Yoshikazu Ninomiya and Masayoshi Higuchi
Molecules 2020, 25(22), 5261; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25225261 - 11 Nov 2020
Cited by 6 | Viewed by 2061
Abstract
A heterobimetallic supramolecular polymer (polyRuFe) with alternately complexed Ru(II) and Fe(II) is prepared following a stepwise synthetic route through harnessing first the strongly binding metal ion Ru(II) and then the weakly binding metal ion Fe(II). A high yield of product is achieved in [...] Read more.
A heterobimetallic supramolecular polymer (polyRuFe) with alternately complexed Ru(II) and Fe(II) is prepared following a stepwise synthetic route through harnessing first the strongly binding metal ion Ru(II) and then the weakly binding metal ion Fe(II). A high yield of product is achieved in each step. The heterometal ions are incorporated into the polymer chain in identical coordination environments formed by two 2,2′:6′,2″-terpyridine moieties. Characterization is accomplished by NMR spectroscopy, MALDI–TOF mass spectrometry, UV–Vis spectroscopy, and cyclic voltammetry. PolyRuFe shows a wide optical window (λ = 311–577 nm) and a broad distinct reversible redox nature of two types, originated from the coupling of the two heterometallic segments into the polymer chain. Such characteristics of polyRuFe suggest its potential for various electrochemical and electro-optical applications. Full article
(This article belongs to the Special Issue Coordination Programming for Electro-, Magneto-, and Photofunctional Molecular Systems: A Theme Issue in Honor of Prof. Dr. Hiroshi Nishihara)
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