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Earth Abundant Transition Metals in Chemical Sensors and Actuators

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A special issue of Sustainability (ISSN 2071-1050). This special issue belongs to the section "Sustainable Chemical Engineering and Technology".

Deadline for manuscript submissions: closed (30 June 2021) | Viewed by 11142

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Special Issue Editors

Dr. Paulo Nuno Martinho

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Guest Editor

Centro de Química e Bioquímica and BioISI-Biosystems & Integrative Sciences Institute, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal
Interests: molecular magnetism in Fe(III) and Mn(III) compounds; elf-assembly and materials development in coordination compounds; electro- and photo-chemical conversion of small molecules with first-row transition metals; materials development for small molecule activation; electronic and photochemical properties in coordination compounds; biomimetic chemistry of Iron and Molybdenum

Dr. Sara Realista

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Guest Editor

ITQB NOVA, Instituto de Tecnologia Química e Biológica, Universidade Nova de Lisboa, Av. da República, 2780-157 Oeiras Portugal
Interests: synthesis; inorganic chemistry; 3d metals; electrochemistry; catalysis; photocatalysis; electrocalaysis

Special Issue Information

Dear Colleagues,

The development of improved sensing and actuating molecules and materials that are triggered by light, temperature or electricity are important for achieving more sustainable processes and, therefore, a more sustainable society. These systems play a key role in sustainable chemistry and improvements are attained when expensive metals are replaced by earth abundant and readily available transition metals. This Special Issue aims to showcase the recent developments in the field of photo-, thermo-, and electrochemical sensors and actuators with earth-abundant metal complexes and materials. Original research articles, short communications, and reviews covering all different aspects of synthesis of complexes and materials with first-row transition metals, photocatalysis, electrocatalysis, photo- and electroactivated chemical processes, mechanistic studies, photoactivated magnetic molecules, and thermoresponsive magnetic molecules are invited. Manuscripts submitted for this Special Issue are subject to a peer review procedure, with the aim of fast and widespread dissemination.

The topics covered in the Special Issue include but are not limited to:

Synthesis (e.g., organic, inorganic)
Materials (e.g., nanoparticles, carbon-based, thin films)
Catalysis (homogeneous and heterogeneous)
Sensors (magnetic, thermal, and electrochemical)
Applications (e.g., small molecule conversion, coupling reactions, oxidation, and reduction reactions, displays, memories, artificial muscles).

Dr. Paulo Nuno Martinho
Dr. Sara Realista
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. Sustainability 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 2400 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

photocatalysis
electrocatalysis
green chemistry
spin crossover
homogeneous catalysis
heterogeneous catalysis
nanocatalysis
surface reactions
mechanistic studies
light-induced spin state trapping
chemical sensors
chemical actuators

Published Papers (4 papers)

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Research

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12 pages, 2503 KiB

Open AccessArticle

Cryptand-Functionalized Highly Oriented Pyrolytic Graphite Electrodes

by Marcos A. Bento, Sara Realista, Ana S. Viana, Ana M. Ferraria and Paulo N. Martinho

Sustainability 2021, 13(8), 4158; https://doi.org/10.3390/su13084158 - 8 Apr 2021

Cited by 3 | Viewed by 2071

Abstract

Reproducible materials that have detection properties towards a certain molecule are very important for applications in the fabrication of devices. Among all the substrates that are used, highly oriented pyrolytic graphite allows to clearly image a monolayer. On the other hand, cryptand molecules are versatile because they can sense certain analytes with high selectivity. The highly oriented pyrolytic graphite electrode was first functionalized with an aryl bearing a bromine or an alkyne group to further attach cryptand molecules to its surface. The functionalization was performed through the electroreduction of aryl diazonium salts. While functionalization with an aryl-bromine produced a 20 nm-thick dendritic layer, functionalization of the surface with an aryl bearing a terminal alkyne produced a 9.7 nm-thick multilayer. However, if the diazonium salt is prepared in situ, a 0.9 nm monolayer with aryl–alkyne groups is formed. The alkyne functionalized electrode reacted with a bromo-cryptand through a Sonogashira C–C coupling reaction yielding electrodes functionalized with cryptands. These were immersed in a solution of a Co(II) salt resulting in Co(II)-cryptate modified electrodes, highlighting the ability of the cryptands’ modified electrode to sense metal ions. The electrode surface was analyzed by X-ray photoelectron spectroscopy after each modification step, which confirmed the successful functionalization of the substrate with both the cryptand and the cryptate. Cyclic voltammetry studies showed stable current response after approximately six cycles. Different reduction processes were detected for both cryptand (−1.40 V vs. SCE) and cryptate (−1.22 V vs. SCE) modified highly oriented pyrolytic graphite. Full article

(This article belongs to the Special Issue Earth Abundant Transition Metals in Chemical Sensors and Actuators)

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18 pages, 4766 KiB

Open AccessArticle

New Bis-Pyrazole-Bis-Acetate Based Coordination Complexes: Influence of Counter-Anions and Metal Ions on the Supramolecular Structures

by Afaf Oulmidi, Smaail Radi, Haralampos N. Miras, Nayarassery N. Adarsh and Yann Garcia

Sustainability 2021, 13(1), 288; https://doi.org/10.3390/su13010288 - 30 Dec 2020

Cited by 6 | Viewed by 2439

Abstract

A new flexible bis-pyrazol-bis-acetate ligand, diethyl 2,2’-(pyridine-2,6-diylbis (5-methyl-1H-pyrazole-3,1-diyl))diacetate (L), has been synthesised, and three coordination complexes, namely, [Zn(L)₂](BF₄)₂ (1), [MnLCl₂] (2) and [CdLCl₂] (3) have been obtained. All ligands and complexes were characterised by IR, mass spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction. Single crystal X-ray diffraction experiment revealed that the primary supramolecular building block of 1 is a hexagonal chair shaped 0D hydrogen bonded synthon (stabilised by C–H∙∙∙O hydrogen bonding and C=O∙∙∙π interactions), which further built into a 2D corrugated sheet-like architecture having a 3-c net honeycomb topology, and finally extended to a 3D hydrogen bonded network structure having a five nodal 1,3,3,3,7-c net, through C–H∙∙∙F interactions. On the other hand, the two crystallographically independent molecules of 2 exhibited two distinct supramolecular structures such as 2D hydrogen bonded sheet structure and 1D zigzag hydrogen bonded chain, sustained by C–H∙O and C–H∙∙∙Cl interactions, which are further self-assembled into a 3,4-c network structure, and 3 showed a 2D hydrogen bonded sheet structure. The supramolecular structural diversity in these complexes is due to the different conformations adopted by the ligands, which are mainly induced by different metal ions with coordination environments controlled by different anions. Hirshfeld surface analysis was explored for the qualitative and quantitative analysis of the supramolecular interactions. Full article

(This article belongs to the Special Issue Earth Abundant Transition Metals in Chemical Sensors and Actuators)

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Graphical abstract

11 pages, 5010 KiB

Open AccessArticle

Crystallisation-Induced Emission Enhancement in Zn(II) Schiff Base Complexes with a Tuneable Emission Colour

by Declan J. L. Golding, Nicholas Carter, David Robinson and Anthony J. Fitzpatrick

Sustainability 2020, 12(22), 9599; https://doi.org/10.3390/su12229599 - 18 Nov 2020

Cited by 1 | Viewed by 2139

Abstract

Four Zn(II) Schiff base complexes that exhibit crystallisation-induced emission enhancement (CIEE) are presented. There is an intermolecular dimerisation through the hydrogen bonding of the mixed phenol/phenolate donors. The choice of ligand also determines the emission wavelength. The complexes have been investigated using experimental [...] Read more.

(This article belongs to the Special Issue Earth Abundant Transition Metals in Chemical Sensors and Actuators)

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Review

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50 pages, 11743 KiB

Open AccessReview

Spin Crossover in 3D Metal Centers Binding Halide-Containing Ligands: Magnetism, Structure and Computational Studies

by Paulo N. Martinho, Frederico F. Martins, Nuno A. G. Bandeira and Maria José Calhorda

Sustainability 2020, 12(6), 2512; https://doi.org/10.3390/su12062512 - 23 Mar 2020

Cited by 11 | Viewed by 3879

Abstract

The capability of a given substance to change its spin state by the action of a stimulus, such as a change in temperature, is by itself a very challenging property. Its interest is increased by the potential applications and the need to find sustainable functional materials. 3D transition metal complexes, mainly with octahedral geometry, display this property when coordinated to particular sets of ligands. The prediction of this behavior has been attempted by many authors. It is, however, made very difficult because spin crossover (SCO), as it is called, occurs most often in the solid state, where besides complexes, counter ions, and solvents are also present in many cases. Intermolecular interactions definitely play a major role in SCO. In this review, we decided to analyze SCO in mono- and binuclear transition metal complexes containing halogens as ligands or as substituents of the ligands. The aim was to try and find trends in the properties which might be correlated to halogen substitution patterns. Besides a revision of the properties, we analyzed structures and other information. We also tried to build a simple model to run Density Functional Theory (DFT) calculations and calculate several parameters hoping to find correlations between calculated indices and SCO data. Although there are many experimental studies and single-crystal X-ray diffraction structures, there are only few examples with the F, Cl, Br and series. When their intermolecular interactions were not very different, T_1/2 (temperature with 50% high spin and 50% low spin states) usually increased with the calculated ligand field parameter (Δ_oct) within a given family. A way to predict SCO remains elusive. Full article

(This article belongs to the Special Issue Earth Abundant Transition Metals in Chemical Sensors and Actuators)

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