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Recent Advances in Supramolecular Organometallic Chemistry
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Recent Advances in Supramolecular Organometallic Chemistry

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

Deadline for manuscript submissions: closed (31 March 2022) | Viewed by 14625

Special Issue Editor

Dr. Susana Ibáñez Maella

E-Mail Website
Guest Editor
Institute of Advanced Materials (INAM), Universitat Jaume I, Castellon de la Plana, Spain
Interests: N-heterocyclic carbenes; organometallics chemistry; supramolecular coordination complexes; metallo-tweezers; self-sorting; host–guest systems; homogeneous catalysis

Special Issue Information

Dear Colleagues,

Supramolecular chemistry is the domain of chemistry beyond molecules, focusing on the chemical systems made up of a discrete number of assembled molecular subunits or components. Numerous examples exist, whereby weak interactions, such as hydrogen bonding, van der Waals, π–π stacking, dipole–dipole and metal coordination direct the organization of the resulting self-assembled structures giving rise to complex architectures with a large number of potential applications from materials technology, sensing, molecular recognition, catalysis, imprinting, molecular machines, etc.

Within the field of supramolecular chemistry, it is necessary to emphasize the importance of this field of metallosupramolecular chemistry, which, it has been demonstrated, is clearly dominated using O-, N-, and P-donor Werner-type polydentate ligands. These molecular architectures are of high interest because of their wide range of applications, which include molecular encapsulation, stabilization of reactive species, supramolecular catalysis, and drug delivery, among others. Only recently, organometallic ligands have allowed the preparation of a variety of supramolecular coordination complexes, and the term supramolecular organometallic complexes (SOCs) is gaining space within the field of metallosupramolecular chemistry.

The present Special Issue will cover some of the recent aspects of supramolecular organometallic field, showing the different variety of systems involved in this field as well as their novel applications.

Dr. Susana Ibáñez Maella
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

  • supramolecular chemistry
  • weak interactions
  • self-sorting
  • host–guest systems
  • metallo-ligands
  • metallo-tweezers

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Published Papers (5 papers)

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Research

10 pages, 1727 KiB  
Communication
The New Di-Gold Metallotweezer Based on an Alkynylpyridine System
by Susana Ibáñez
Molecules 2022, 27(12), 3699; https://doi.org/10.3390/molecules27123699 - 9 Jun 2022
Viewed by 1597
Abstract
We developed a simple method to prepare one gold-based metallotweezer with two planar Au-pyrene-NHC arms bound by a 2,6-bis(3-ethynyl-5-tert-butylphenyl)pyridine unit. This metallotweezer is able to bind a series of polycyclic aromatic hydrocarbons through the π-stacking interactions between the polyaromatic guests and the pyrene [...] Read more.
We developed a simple method to prepare one gold-based metallotweezer with two planar Au-pyrene-NHC arms bound by a 2,6-bis(3-ethynyl-5-tert-butylphenyl)pyridine unit. This metallotweezer is able to bind a series of polycyclic aromatic hydrocarbons through the π-stacking interactions between the polyaromatic guests and the pyrene moieties of the NHC ligands. The metallotweezer was also used as a host for the encapsulation of planar metal complexes, such as the Au(III) complex [Au(C^N^C)(C≡CC6H4-OCH3-p)], for which there is a large binding constant of 946 M−1. Full article
(This article belongs to the Special Issue Recent Advances in Supramolecular Organometallic Chemistry)
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24 pages, 5119 KiB  
Article
Molecular Docking, DFT Calculations, Effect of High Energetic Ionizing Radiation, and Biological Evaluation of Some Novel Metal (II) Heteroleptic Complexes Bearing the Thiosemicarbazone Ligand
by Ehab M. Abdalla, Safaa S. Hassan, Hussein H. Elganzory, Samar A. Aly and Heba Alshater
Molecules 2021, 26(19), 5851; https://doi.org/10.3390/molecules26195851 - 27 Sep 2021
Cited by 29 | Viewed by 2736
Abstract
New Pb(II), Mn(II), Hg(II), and Zn(II) complexes, derived from 4-(4-chlorophenyl)-1-(2-(phenylamino)acetyl)thiosemicarbazone, were synthesized. The compounds with general formulas, [Pb(H2L)2(OAc)2]ETOH.H2O, [Mn(H2L)(HL)]Cl, [Hg2(H2L)(OH)SO4], and [Zn(H2L)(HL)]Cl, were characterized by [...] Read more.
New Pb(II), Mn(II), Hg(II), and Zn(II) complexes, derived from 4-(4-chlorophenyl)-1-(2-(phenylamino)acetyl)thiosemicarbazone, were synthesized. The compounds with general formulas, [Pb(H2L)2(OAc)2]ETOH.H2O, [Mn(H2L)(HL)]Cl, [Hg2(H2L)(OH)SO4], and [Zn(H2L)(HL)]Cl, were characterized by physicochemical and theoretical studies. X-ray diffraction studies showed a decrease in the crystalline size of compounds that were exposed to gamma irradiation (γ-irradiation). Thermal studies of the synthesized complexes showed thermal stability of the Mn(II) and Pb(II) complexes after γ-irradiation compared to those before γ–irradiation, while no changes in the Zn(II) and Hg(II) complexes were observed. The optimized geometric structures of the ligand and metal complexes are discussed regarding density functional theory calculations (DFT). The antimicrobial activities of the ligand and metal complexes against several bacterial and fungal stains were screened before and after irradiation. The Hg(II) complex has shown excellent antibacterial activity before and after γ-irradiation. In vitro cytotoxicity screening of the ligand and the Mn(II) and Zn(II) complexes before and after γ-irradiation disclosed that both the ligand and Mn(II) complex exhibited higher activity against human liver (Hep-G2) than Zn(II). Molecular docking was performed on the active site of MK-2 and showed good results. Full article
(This article belongs to the Special Issue Recent Advances in Supramolecular Organometallic Chemistry)
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25 pages, 7030 KiB  
Article
A “Pretender” Croconate-Bridged Macrocyclic Tetraruthenium Complex: Sizable Redox Potential Splittings despite Electronically Insulated Divinylphenylene Diruthenium Entities
by Nils Rotthowe, Michael Linseis, Lars Vogelsang, Nicole Orth, Ivana Ivanović-Burmazović and Rainer F. Winter
Molecules 2021, 26(17), 5232; https://doi.org/10.3390/molecules26175232 - 29 Aug 2021
Cited by 4 | Viewed by 3081
Abstract
Careful optimization of the reaction conditions provided access to the particularly small tetraruthenium macrocycle 2Ru2Ph-Croc, which is composed out of two redox-active divinylphenylene-bridged diruthenium entities {Ru}-1,4-CH=CH-C6H4-CH=CH-{Ru} (Ru2Ph; {Ru} = Ru(CO)Cl(PiPr3 [...] Read more.
Careful optimization of the reaction conditions provided access to the particularly small tetraruthenium macrocycle 2Ru2Ph-Croc, which is composed out of two redox-active divinylphenylene-bridged diruthenium entities {Ru}-1,4-CH=CH-C6H4-CH=CH-{Ru} (Ru2Ph; {Ru} = Ru(CO)Cl(PiPr3)2) and two likewise redox-active and potentially non-innocent croconate linkers. According to single X-ray diffraction analysis, the central cavity of 2Ru2Ph-Croc is shielded by the bulky PiPr3 ligands, which come into close contact. Cyclic voltammetry revealed two pairs of split anodic waves in the weakly ion pairing CH2Cl2/NBu4BArF24 (BArF24 = [B{C6H3(CF3)2-3,5}4]− electrolyte, while the third and fourth waves fall together in CH2Cl2/NBu4PF6. The various oxidized forms were electrogenerated and scrutinized by IR and UV/Vis/NIR spectroscopy. This allowed us to assign the individual oxidations to the metal-organic Ru2Ph entities within 2Ru2Ph-Croc, while the croconate ligands remain largely uninvolved. The lack of specific NIR bands that could be assigned to intervalence charge transfer (IVCT) in the mono- and trications indicates that these mixed-valent species are strictly charge-localized. 2Ru2Ph-Croc is hence an exemplary case, where stepwise IR band shifts and quite sizable redox splittings between consecutive one-electron oxidations would, on first sight, point to electronic coupling, but are exclusively due to electrostatic and inductive effects. This makes 2Ru2Ph-Croc a true “pretender”. Full article
(This article belongs to the Special Issue Recent Advances in Supramolecular Organometallic Chemistry)
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Graphical abstract

12 pages, 23842 KiB  
Article
Investigation of the Amide Linkages on Cooperative Supramolecular Polymerization of Organoplatinum(II) Complexes
by Mingliang Gui, Yifei Han, Hua Zhong, Rui Liao and Feng Wang
Molecules 2021, 26(9), 2832; https://doi.org/10.3390/molecules26092832 - 10 May 2021
Cited by 3 | Viewed by 3063
Abstract
Cooperative supramolecular polymerization of π-conjugated compounds into one-dimensional nanostructures has received tremendous attentions in recent years. It is commonly achieved by incorporating amide linkages into the monomeric structures, which provide hydrogen bonds for intermolecular non-covalent complexation. Herein, the effect of amide linkages is [...] Read more.
Cooperative supramolecular polymerization of π-conjugated compounds into one-dimensional nanostructures has received tremendous attentions in recent years. It is commonly achieved by incorporating amide linkages into the monomeric structures, which provide hydrogen bonds for intermolecular non-covalent complexation. Herein, the effect of amide linkages is elaborately studied, by comparing supramolecular polymerization behaviors of two structurally similar monomers with the same platinum(II) acetylide cores. As compared to the N-phenyl benzamide linkages, N-[(1S)-1-phenylethyl] benzamide linkages give rise to effective chirality transfer behaviors due to the closer distances between the chiral units and the platinum(II) acetylide core. They also provide stronger intermolecular hydrogen bonding strength, which consequently brings higher thermo-stability and enhanced gelation capability for the resulting supramolecular polymers. Supramolecular polymerization is further strengthened by varying the monomers from monotopic to ditopic structures. Hence, with the judicious modulation of structural parameters, the current study opens up new avenues for the rational design of supramolecular polymeric systems. Full article
(This article belongs to the Special Issue Recent Advances in Supramolecular Organometallic Chemistry)
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14 pages, 3755 KiB  
Article
Using Room Temperature Phosphorescence of Gold(I) Complexes for PAHs Sensing
by Marian Rosental, Richard N. Coldman, Artur J. Moro, Inmaculada Angurell, Rosa M. Gomila, Antonio Frontera, João Carlos Lima and Laura Rodríguez
Molecules 2021, 26(9), 2444; https://doi.org/10.3390/molecules26092444 - 22 Apr 2021
Cited by 8 | Viewed by 2712
Abstract
The synthesis of two new phosphane-gold(I)–napthalimide complexes has been performed and characterized. The compounds present luminescent properties with denoted room temperature phosphorescence (RTP) induced by the proximity of the gold(I) heavy atom that favors intersystem crossing and triplet state population. The emissive properties [...] Read more.
The synthesis of two new phosphane-gold(I)–napthalimide complexes has been performed and characterized. The compounds present luminescent properties with denoted room temperature phosphorescence (RTP) induced by the proximity of the gold(I) heavy atom that favors intersystem crossing and triplet state population. The emissive properties of the compounds together with the planarity of their chromophore were used to investigate their potential as hosts in the molecular recognition of different polycyclic aromatic hydrocarbons (PAHs). Naphthalene, anthracene, phenanthrene, and pyrene were chosen to evaluate how the size and electronic properties can affect the host:guest interactions. Stronger affinity has been detected through emission titrations for the PAHs with extended aromaticity (anthracene and pyrene) and the results have been supported by DFT calculation studies. Full article
(This article belongs to the Special Issue Recent Advances in Supramolecular Organometallic Chemistry)
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