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Special Issue "Coordination Chemistry for Devices and Functional Materials"

A special issue of Molecules (ISSN 1420-3049).

Deadline for manuscript submissions: 31 August 2018

Special Issue Editors

Guest Editor
Prof. Dr. Piersandro Pallavicini

Dipartimento di Chimica, Università di Pavia, viale Taramelli, 12, 27100 Pavia, Italy
Website | E-Mail
Interests: coordination chemistry; supramolecular chemistry; fluorescent sensors; inorganic nanoparticles; antibacterial inorganic materials; photothermal nanoparticles
Guest Editor
Dr. Giacomo Dacarro

Dipartimento di Chimica, Università di Pavia, viale Taramelli, 12, 27100 Pavia, Italy
Website | E-Mail
Interests: coordination chemistry; supramolecular chemistry; inorganic nanoparticles; surface functionalization; antibacterial inorganic materials; photothermal nanoparticles

Special Issue Information

Dear Colleagues,

We are calling for your significant contributions for the Special Issue: “Coordination Chemistry for Molecular Devices and Functional Materials”. Thanks to the versatility of metal–ligand interactions and thanks to the rich and tunable thermodynamic, kinetic, optical and electrochemical properties of metal complexes, coordinative chemistry allows a powerful and always evolving approach to systems such as molecular devices and functional materials. These range from the single-molecule dimensions to bulk materials and include nanoparticles and functionalized surfaces, while their applications range from the biomedical to the clean energy area.

Accordingly, the Issue will cover the following topics: (i) coordination complexes for molecular, supramolecular and nano devices; (ii) sensing and tracking metal cations and molecules through coordinative interactions; (iii) metal complexes for biomedical applications; (iv) functional bulk materials based on coordinative interactions.

I hope this topic is of interest to you as we are taking the opportunity to look at recent developments as well as exploring the future scope in this field.

Prof. Dr. Piersandro Pallavicini
Prof. Dr. Giacomo Dacarro
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 papers will be 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 monthly 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 1800 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

  • Molecular sensors;
  • Molecular devices
  • Coordinative materials
  • Functional nanoparticles
  • Metal complexes
  • Luminescent complexes
  • Metal complexes in medicine

Published Papers (6 papers)

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Research

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Open AccessArticle Confinement Effects on Chemical Equilibria: Pentacyano(Pyrazine)Ferrate(II) Stability Changes within Nanosized Droplets of Water
Molecules 2018, 23(4), 858; https://doi.org/10.3390/molecules23040858
Received: 5 March 2018 / Revised: 30 March 2018 / Accepted: 4 April 2018 / Published: 9 April 2018
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Abstract
Nanoscale confinement is known to impact properties of molecules and we observed changes in the reactivity of an iron coordination complex, pentacyano(pyrazine)ferrate(II). The confinement of two coordination complexes in a sodium AOT/isooctane reverse micellar (RM) water droplet was found to dramatically increase the
[...] Read more.
Nanoscale confinement is known to impact properties of molecules and we observed changes in the reactivity of an iron coordination complex, pentacyano(pyrazine)ferrate(II). The confinement of two coordination complexes in a sodium AOT/isooctane reverse micellar (RM) water droplet was found to dramatically increase the hydrolysis rate of [Fe(CN)5pyz]3− and change the monomer-dimer equilibria between [Fe(CN)5pyz]3− and [Fe2(CN)10pyz]6−. Combined UV-Vis and 1H-NMR spectra of these complexes in RMs were analyzed and the position of the monomer-dimer equilibrium and the relative reaction times were determined at three different RM sizes. The data show that the hydrolysis rates (loss of pyrazine) are dramatically enhanced in RMs over bulk water and increase as the size of the RM decreases. Likewise, the monomer-dimer equilibrium changes to favor the formation of dimer as the RM size decreases. We conclude that the effects of the [Fe(CN)5pyz]3− stability is related to its solvation within the RM. Full article
(This article belongs to the Special Issue Coordination Chemistry for Devices and Functional Materials)
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Open AccessArticle Preparation of Ruthenium Dithiolene Complex/Polysiloxane Films and Their Responses to CO Gas
Molecules 2018, 23(4), 845; https://doi.org/10.3390/molecules23040845
Received: 6 March 2018 / Revised: 3 April 2018 / Accepted: 4 April 2018 / Published: 7 April 2018
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Abstract
To develop advanced materials using metal complexes, it is better to prepare metal complexes contained in composite or hybrid films. To achieve this purpose, we synthesized ruthenium complexes with dihalogen-substituted benzendithiolate ligands, [(η6-C6Me6)Ru(S2C6H
[...] Read more.
To develop advanced materials using metal complexes, it is better to prepare metal complexes contained in composite or hybrid films. To achieve this purpose, we synthesized ruthenium complexes with dihalogen-substituted benzendithiolate ligands, [(η6-C6Me6)Ru(S2C6H2X2)] (X = F, 3,6-Cl, Br, 4,5-Cl), 1b1e. We also investigated preparation of 1c or 1e containing polysiloxane composite films and their reactivity to CO gas. All ruthenium complexes 1b1e reacted with CO gas, and carbonyl ligand adducts 2b2e were generated. Ruthenium complexes 1b1e show two strong absorption peaks around 550 and 420 nm. After exposure to CO gas, these absorption peaks were immediately decreased without a peak shift. A similar trend was observed in 1c or 1e containing polysiloxane composite films. These results indicate that 1c and 1e were easily converted into 2c and 2e, both in the solution and the polysiloxane film during CO gas exposure. Full article
(This article belongs to the Special Issue Coordination Chemistry for Devices and Functional Materials)
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Open AccessFeature PaperArticle Recognition of AMP, ADP and ATP through Cooperative Binding by Cu(II) and Zn(II) Complexes Containing Urea and/or Phenylboronic—Acid Moieties
Molecules 2018, 23(2), 479; https://doi.org/10.3390/molecules23020479
Received: 25 January 2018 / Revised: 16 February 2018 / Accepted: 20 February 2018 / Published: 22 February 2018
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Abstract
We report a series of Cu(II) and Zn(II) complexes with different ligands containing a dipicolyl unit functionalized with urea groups that may contain or not a phenylboronic acid function. These complexes were designed for the recognition of phosphorylated anions through coordination to the
[...] Read more.
We report a series of Cu(II) and Zn(II) complexes with different ligands containing a dipicolyl unit functionalized with urea groups that may contain or not a phenylboronic acid function. These complexes were designed for the recognition of phosphorylated anions through coordination to the metal ion reinforced by hydrogen bonds involving the anion and NH groups of urea. The complexes were isolated and several adducts with pyrophosphate were characterized using X-ray diffraction measurements. Coordination of one of the urea nitrogen atoms to the metal ion promoted the hydrolysis of the ligands containing 1,3-diphenylurea units, while ligands bearing 1-ethyl-3-phenylurea groups did not hydrolyze significantly at room temperature. Spectrophotometric titrations, combined with 1H and 31P NMR studies, were used in investigating the binding of phosphate, pyrophosphate (PPi), and nucleoside 5′-polyphosphates (AMP, ADP, ATP, CMP, and UMP). The association constants determined in aqueous solution (pH 7.0, 0.1 M MOPS) point to a stronger association with PPi, ADP, and ATP as compared with the anions containing a single phosphate unit. The [CuL4]2+ complex shows important selectivity for pyrophosphate (PPi) over ADP and ATP. Full article
(This article belongs to the Special Issue Coordination Chemistry for Devices and Functional Materials)
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Open AccessArticle Gold and Nickel Extended Thiophenic-TTF Bisdithiolene Complexes
Molecules 2018, 23(2), 424; https://doi.org/10.3390/molecules23020424
Received: 19 January 2018 / Revised: 5 February 2018 / Accepted: 9 February 2018 / Published: 14 February 2018
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Abstract
Gold and nickel bisdithiolene complexes with methyl and tert-butyl substituted thiophenetetrathiafulavalenedithiolate ligands (α-mtdt and α-tbtdt) were prepared and characterized. These complexes were obtained, under anaerobic conditions, as tetrabutylammonium salts. The diamagnetic gold monoanion (n-Bu4N)[Au(α-mtdt)2] (3
[...] Read more.
Gold and nickel bisdithiolene complexes with methyl and tert-butyl substituted thiophenetetrathiafulavalenedithiolate ligands (α-mtdt and α-tbtdt) were prepared and characterized. These complexes were obtained, under anaerobic conditions, as tetrabutylammonium salts. The diamagnetic gold monoanion (n-Bu4N)[Au(α-mtdt)2] (3) and nickel dianionic species (n-Bu4N)x[Ni(α-mtdt)2] (x = 1,2) (4) were similar to the related non-substituted extended thiophenic-TTF (TTF = tetrathiafulvalene) bisdithiolenes. However the introduction of the large, bulky substituent tert-butyl, led to the formation of a Au (I) dinuclear complex, (n-Bu4N)2[Au2(α-tbtdt)2] (5). The neutral methyl substituted gold and nickel complexes were easily obtained through air or iodine exposure as polycrystalline or amorphous fine powder. [Au(α-mtdt)2] (6) and [Ni(α-mtdt)2] (7) polycrystalline samples display properties of a metallic system with a room temperature electrical conductivity of 0.32 S/cm and ≈4 S/cm and a thermoelectric power of ≈5 µV/K and ≈32 µV/K, respectively. While [Au(α-mtdt)2] (6) presented a Pauli-like magnetic susceptibility typical of conducting systems, in [Ni(α-mtdt)2] (7) large magnetic susceptibilities indicative of high spin states were observed. Both electric transport properties and magnetic properties for gold and nickel [M(α-mtdt)2] are indicative that these compounds are single component molecular conductors. Full article
(This article belongs to the Special Issue Coordination Chemistry for Devices and Functional Materials)
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Open AccessArticle Functional Magnetic Mesoporous Silica Microparticles Capped with an Azo-Derivative: A Promising Colon Drug Delivery Device
Molecules 2018, 23(2), 375; https://doi.org/10.3390/molecules23020375
Received: 15 January 2018 / Revised: 31 January 2018 / Accepted: 8 February 2018 / Published: 10 February 2018
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Abstract
Magnetic micro-sized mesoporous silica particles were used for the preparation of a gated material able to release an entrapped cargo in the presence of an azo-reducing agent and, to some extent, at acidic pH. The magnetic mesoporous microparticles were loaded with safranin O
[...] Read more.
Magnetic micro-sized mesoporous silica particles were used for the preparation of a gated material able to release an entrapped cargo in the presence of an azo-reducing agent and, to some extent, at acidic pH. The magnetic mesoporous microparticles were loaded with safranin O and the external surface was functionalized with an azo derivative 1 (bearing a carbamate linkage) yielding solid S1. Aqueous suspensions of S1 at pH 7.4 showed negligible safranin O release due to the presence of the bulky azo derivative attached onto the external surface of the inorganic scaffold. However, in the presence of sodium dithionite (azoreductive agent), a remarkable safranin O delivery was observed. At acidic pH, a certain safranin O release from S1 was also found. The pH-triggered safranin O delivery was ascribed to the acid-induced hydrolysis of the carbamate moiety that linked the bulky azo derivatives onto the mesoporous inorganic magnetic support. The controlled release behavior of S1 was also tested using a model that simulated the gastro intestinal tract. Full article
(This article belongs to the Special Issue Coordination Chemistry for Devices and Functional Materials)
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Review

Jump to: Research

Open AccessReview Outlook on the Application of Metal-Liganded Bioactives for Stimuli-Responsive Release
Molecules 2017, 22(12), 2065; https://doi.org/10.3390/molecules22122065
Received: 13 October 2017 / Revised: 13 November 2017 / Accepted: 25 November 2017 / Published: 26 November 2017
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Abstract
Direct metal-liganded bioactive coordination complexes are known to be sensitive to stimuli such as pH, light, ion activation, or redox cues. This results in the controlled release of the bioactive(s). Compared to other drug delivery strategies based on metal complexation, this type of
[...] Read more.
Direct metal-liganded bioactive coordination complexes are known to be sensitive to stimuli such as pH, light, ion activation, or redox cues. This results in the controlled release of the bioactive(s). Compared to other drug delivery strategies based on metal complexation, this type of coordination negates a multi-step drug loading methodology and offers customized physiochemical properties through judicious choice of modulating ancillary ligands. Bioactive release depends on simple dissociative kinetics. Nonetheless, there are challenges encountered when translating the pure coordination chemistry into the biological and physiological landscape. The stability of the metal–bioactive complex in the biological milieu may be compromised, disrupting the stimuli-responsive release mechanism, with premature release of the bioactive. Research has therefore progressed to the incorporation of metal-liganded bioactives with established drug delivery strategies to overcome these limitations. This review will highlight and critically assess current research interventions in order to predict the direction that pharmaceutical scientists could pursue to arrive at tailored and effective metal-liganded bioactive carriers for stimuli-responsive drug release. Full article
(This article belongs to the Special Issue Coordination Chemistry for Devices and Functional Materials)
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Planned Papers

The below list represents only planned manuscripts. Some of these manuscripts have not been received by the Editorial Office yet. Papers submitted to MDPI journals are subject to peer-review.

Type: review.
Title: Prussian Blue Nanoparticles as a versatile photothermal tool
Abstract: Prussian blue (PB) is a coordination polymer studied since the early 18th century, hystorically known as a pigment. PB can be prepared in colloidal form with a straightforward synthesis. It has a strong charge-transfer absorption centered at  700nm, with a large tail in the Near-IR range. Irradiation of this band results in thermal relaxation and can be exploited to generate a local hyperthermia ny irradiating in the so-called bio-transparent Near-IR window. PB nanoparticles are fully biocompatible (PB has already been approved by FDA) and biodegradable, this making them ideal candidates for in vivo use. While papers based on the imaging, drug-delivery and absorbing properties of PB nanoparticles have appeared and have been reviewed in the past decades, a very recent interest is flourishing with the use of PB nanoparticles as photothermal agents in biomedical applications. This review summarizes the syntheses and the optical features of PB nanoparticles in relation to their photothermal use and describes the state of the art of PB nanoparticles as photothermal agents, also in combination with diagnostic techniques.
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