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Zn(II) and Cd(II) Coordination Polymers: Advances and Perspectives

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

Deadline for manuscript submissions: closed (31 October 2022) | Viewed by 19217

Special Issue Editors


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Guest Editor
Institute of Applied Physics, Moldova State University, 5 MD2028, Chisinau, Moldova
Interests: coordination chemistry of d10 transition metals; single crystal X-ray crystallography; crystal engineering; fluorescence; supramolecular chemistry; structure and properties of molecular materials; intermolecular interactions; H-bonding; self-assembly phenomena; guest inclusion
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Special Issue Information

Dear Colleagues,

In mid-1990x the first Zn(II) (Zaworotko et al, 1995; Yaghi et al., 1999) and Cd(II) (Fujita et al., 1994) coordination networks were reported. In the 21st  century the coordination polymers based on the closed-shell d10 metals like Zn and Cd remain in focus of coordination and supramolecular chemistry, crystal engineering and materials science. Alongside the rigid MOF structures, the flexible and dynamic stimuli  responsive 1D and 2D coordination polymers keep on the hot topic and the subject of cut-edge current studies. Among the novel intriguing approaches in this field the organization of CPs on surfaces with possible technological applications in nanoelectronics, spintronics or nanosensing; obtaining the liquid/glassy states in metallo-organic coordination polymers by design principles; registration of photochromic behavior as prerequisite for the inkless and erasable printing media can be mentioned as only a few examples.

Since the library of Zn(II) and Cd(II) coordination networks is numerous and continues growing rapidly demonstrating fascinated crystal structures and impressive properties, the Editorial Board of Molecules, thus, decided to devote a Special Issue of the journal to this topic. This Special Issue is expected to provide an excellent platform to report results that highlight the synthesis, crystal structures in combination with the spectrum of impressive properties of Zn(II) and Cd(II) coordination polymers. As Guest Editor, I cordially invite scientists from various fields to submit articles which cover a broad range of subjects in coordination polymer chemistry.

Dr. Marina Fonari
Guest Editor

Dr. Rodica Olar
Co-Guest Editor

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Keywords

  • New eco-friendly synthetic protocols
  • solution crystallization, solid-state grinding, solvent drop grinding
  • Eco-friendly/new linkers
  • mixed-ligand, hybrid organic/inorganic ligand strategies
  • functionalized ligands
  • Crystal engineering guidelines as a pathway for systematic design
  • SC-SC transformations in 1D, 2D, 3D CPs
  • Adsorption/separation processes in1D, 2D, CPs and 3D MOFs
  • Flexibility
  • guest-responsive porous coordination networks
  • Chiral coordination networks in the presence/absence of chiral components
  • The interplay of coordinative, hydrogen bonding, stacking interactions in sustaining crystal stability
  • The fluorescence properties of CPs
  • emission modulation
  • CPs as sensors for hazardous pollutants
  • Rationales for effective multifunctional materials

Published Papers (9 papers)

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Research

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10 pages, 2465 KiB  
Communication
An Interesting Conversion Route of Mononuclear Zinc Complex to Zinc Mixed Carboxylate Coordination Polymer
by Gina Vasile Scăețeanu, Constantin G. Daniliuc, Rodica Olar and Mihaela Badea
Molecules 2023, 28(5), 2011; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules28052011 - 21 Feb 2023
Viewed by 880
Abstract
A complex [Zn(bpy)(acr)2]·H2O (1) was converted in a DMF medium (DMF = N,N′-dimethylformamide) into a coordination polymer [Zn(bpy)(acr)(HCOO)]n (1a) (bpy = 2,2′-bipyridine, and Hacr = acrylic acid), and the species was fully characterized [...] Read more.
A complex [Zn(bpy)(acr)2]·H2O (1) was converted in a DMF medium (DMF = N,N′-dimethylformamide) into a coordination polymer [Zn(bpy)(acr)(HCOO)]n (1a) (bpy = 2,2′-bipyridine, and Hacr = acrylic acid), and the species was fully characterized through a single crystal X-ray diffraction. Additional data were obtained by IR and thermogravimetric analysis. Complex (1a) crystalized the coordination polymer in the space group Pca21 of an orthorhombic system. Structural characterization revealed that Zn(II) adopted a square pyramidal stereochemistry generated by bpy molecules, coordinated by chelate, acrylate, and formate ions as unidentate and bridged, respectively. The presence of both the formate and the acrylate with different coordination modes generated two bands in ranges that were characteristic for the carboxylate vibration modes. Thermal decomposition occurs in two complex steps: it first happens via a bpy release, which is followed by an overlapped process that is associated with acrylate and formate decomposition. The obtained complex is of present interest due to the presence of two different carboxylates in its composition and situation, which is rarely reported in the literature. Full article
(This article belongs to the Special Issue Zn(II) and Cd(II) Coordination Polymers: Advances and Perspectives)
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21 pages, 8209 KiB  
Article
Heteroligand α-Diimine-Zn(II) Complexes with O,N,O′- and O,N,S-Donor Redox-Active Schiff Bases: Synthesis, Structure and Electrochemical Properties
by Ivan V. Smolyaninov, Andrey I. Poddel’sky, Daria A. Burmistrova, Julia K. Voronina, Nadezhda P. Pomortseva, Vasiliy A. Fokin, Ekaterina D. Tselukovskaya, Ivan V. Ananyev, Nadezhda T. Berberova and Igor L. Eremenko
Molecules 2022, 27(23), 8216; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules27238216 - 25 Nov 2022
Cited by 5 | Viewed by 1322
Abstract
A number of novel heteroligand Zn(II) complexes (18) of the general type (Ln)Zn(NN) containing O,N,O′-, O,N,S-donor redox-active Schiff bases and neutral N,N′-chelating ligands (NN) were synthesized. The target Schiff bases LnH2 were obtained as [...] Read more.
A number of novel heteroligand Zn(II) complexes (18) of the general type (Ln)Zn(NN) containing O,N,O′-, O,N,S-donor redox-active Schiff bases and neutral N,N′-chelating ligands (NN) were synthesized. The target Schiff bases LnH2 were obtained as a result of the condensation of 3,5-di-tert-butyl-2-hydroxybenzaldehyde with substituted o-aminophenols or o-aminothiophenol. These ligands with combination with 2,2′-bipyridine, 1,10-phenanthroline, and neocuproine are able to form stable complexes upon coordination with zinc(II) ion. The molecular structures of complexes 4∙H2O, 6, and 8 in crystal state were determined by means of single-crystal X-ray analysis. In the prepared complexes, the redox-active Schiff bases are in the form of doubly deprotonated dianions and act as chelating tridentate ligands. Complexes 6 and 8 possess a strongly distorted pentacoordinate geometry while 4∙H2O is hexacoordinate and contains water molecule coordinated to the central zinc atom. The electrochemical properties of zinc(II) complexes were studied by the cyclic voltammetry. For the studied complexes, O,N,O′- or O,N,S-donor Schiff base ligands are predominantly involved in electrochemical transformations in the anodic region, while the N,N′-coordinated neutral nitrogen donor ligands demonstrate the electrochemical activity in the cathode potential range. A feature of complexes 5 and 8 with sterically hindered tert-butyl groups is the possibility of the formation of relatively stable monocation and monoanion forms under electrochemical conditions. The values of the energy gap between the boundary redox orbitals were determined by electrochemical and spectral methods. The parameters obtained in the first case vary from 1.97 to 2.42 eV, while the optical bang gap reaches 2.87 eV. Full article
(This article belongs to the Special Issue Zn(II) and Cd(II) Coordination Polymers: Advances and Perspectives)
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12 pages, 1334 KiB  
Article
Synthesis of a Chiral 3,6T22-Zn-MOF with a T-Shaped Bifunctional Pyrazole-Isophthalate Ligand Following the Principles of the Supramolecular Building Layer Approach
by Dennis Woschko, Simon Millan, Muhammed-Ali Ceyran, Robert Oestreich and Christoph Janiak
Molecules 2022, 27(17), 5374; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules27175374 - 23 Aug 2022
Cited by 2 | Viewed by 1418
Abstract
The metal–organic framework (MOF) [Zn(Isa-az-tmpz)]·~1–1.5 DMF with the novel T-shaped bifunctional linker 5-(2-(1,3,5-trimethyl-1H-pyrazol-4-yl)azo)isophthalate (Isa-az-tmpz) was obtained as a conglomerate of crystals with varying degrees of enantiomeric excess in the chiral tetragonal space groups P43212 or P4121 [...] Read more.
The metal–organic framework (MOF) [Zn(Isa-az-tmpz)]·~1–1.5 DMF with the novel T-shaped bifunctional linker 5-(2-(1,3,5-trimethyl-1H-pyrazol-4-yl)azo)isophthalate (Isa-az-tmpz) was obtained as a conglomerate of crystals with varying degrees of enantiomeric excess in the chiral tetragonal space groups P43212 or P41212. A topological analysis of the compound resulted in the rare 3,6T22-topology, deviating from the expected rtl-topology, which has been found before in pyrazolate-isophthalate-functionalized MOFs using the supramolecular building layer (SBL) approach. 3,6T22-[Zn(Isa-az-tmpz)]·~1–1.5 DMF is a potentially porous, three-dimensional structure with DMF molecules included in the corrugated channels along the a and b-axis of the as synthesized material. The small trigonal cross-section of about 6 × 4 Å (considering the van der Waals surface) prevents the access of N2 and Ar under cryogenic conditions. After activation, only smaller H2 (at 87 K) and CO2 (at 195 K) are allowed for gas uptakes of 2 mmol g–1 and 5.4 mmol g–1, respectively, in the ultramicroporous material, for which a BET surface area of 496 m2·g–1 was calculated from CO2 adsorption. Thermogravimetric analysis of the compound shows a thermal stability of up to 400 °C. Full article
(This article belongs to the Special Issue Zn(II) and Cd(II) Coordination Polymers: Advances and Perspectives)
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19 pages, 4866 KiB  
Article
Solid-Phase “Self-Hydrolysis” of [Zn(NH3)4MoO4@2H2O] Involving Enclathrated Water—An Easy Route to a Layered Basic Ammonium Zinc Molybdate Coordination Polymer
by Kende Attila Béres, István E. Sajó, György Lendvay, László Trif, Vladimir M. Petruševski, Berta Barta-Holló, László Korecz, Fernanda Paiva Franguelli, Krisztina László, Imre Miklós Szilágyi and László Kótai
Molecules 2021, 26(13), 4022; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26134022 - 30 Jun 2021
Cited by 10 | Viewed by 2365
Abstract
An aerial humidity-induced solid-phase hydrolytic transformation of the [Zn(NH3)4]MoO4@2H2O (compound 1@2H2O) with the formation of [(NH4)xH(1−x)Zn(OH)(MoO4)]n (x = 0.92–0.94) [...] Read more.
An aerial humidity-induced solid-phase hydrolytic transformation of the [Zn(NH3)4]MoO4@2H2O (compound 1@2H2O) with the formation of [(NH4)xH(1−x)Zn(OH)(MoO4)]n (x = 0.92–0.94) coordination polymer (formally NH4Zn(OH)MoO4, compound 2) is described. Based on the isostructural relationship, the powder XRD indicates that the crystal lattice of compound 1@2H2O contains a hydrogen-bonded network of tetraamminezinc (2+) and molybdate (2−) ions, and there are cavities (O4N4(μ-H12) cube) occupied by the two water molecules, which stabilize the crystal structure. Several observations indicate that the water molecules have no fixed positions in the lattice voids; instead, the cavity provides a neighborhood similar to those in clathrates. The @ symbol in the notation is intended to emphasize that the H2O in this compound is enclathrated rather than being water of crystallization. Yet, signs of temperature-dependent dynamic interactions with the wall of the cages can be detected, and 1@2H2O easily releases its water content even on standing and yields compound 2. Surprisingly, hydrolysis products of 1 were observed even in the absence of aerial humidity, which suggests a unique solid-phase quasi-intramolecular hydrolysis. A mechanism involving successive substitution of the ammonia ligands by water molecules and ammonia release is proposed. An ESR study of the Cu-doped compound 2 (2#dotCu) showed that this complex consists of two different Cu2+(Zn2+) environments in the polymeric structure. Thermal decomposition of compounds 1 and 2 results in ZnMoO4 with similar specific surface area and morphology. The ZnMoO4 samples prepared from compounds 1 and 2 and compound 2 in itself are active photocatalysts in the degradation of Congo Red dye. IR, Raman, and UV studies on compounds 1@2H2O and 2 are discussed in detail. Full article
(This article belongs to the Special Issue Zn(II) and Cd(II) Coordination Polymers: Advances and Perspectives)
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15 pages, 5624 KiB  
Article
Crystal Engineering of Schiff Base Zn(II) and Cd(II) Homo- and Zn(II)M(II) (M = Mn or Cd) Heterometallic Coordination Polymers and Their Ability to Accommodate Solvent Guest Molecules
by Olga Danilescu, Paulina N. Bourosh, Oleg Petuhov, Olga V. Kulikova, Ion Bulhac, Yurii M. Chumakov and Lilia Croitor
Molecules 2021, 26(8), 2317; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26082317 - 16 Apr 2021
Cited by 10 | Viewed by 1969
Abstract
Based on solvothermal synthesis, self-assembly of the heptadentate 2,6-diacetylpyridine bis(nicotinoylhydrazone) Schiff base ligand (H2L) and Zn(II) and/or Cd(II) salts has led to the formation of three homometallic [CdL]n (1), {[CdL]∙0.5dmf∙H2O}n (2) and {[ZnL]∙0.5dmf∙1.5H [...] Read more.
Based on solvothermal synthesis, self-assembly of the heptadentate 2,6-diacetylpyridine bis(nicotinoylhydrazone) Schiff base ligand (H2L) and Zn(II) and/or Cd(II) salts has led to the formation of three homometallic [CdL]n (1), {[CdL]∙0.5dmf∙H2O}n (2) and {[ZnL]∙0.5dmf∙1.5H2O}n (3), as well as two heterometallic {[Zn0.75Cd1.25L2]∙dmf∙0.5H2O}n (4) and {[MnZnL2]∙dmf∙3H2O}n coordination polymers. Compound 1 represents a 1D chain, whereas 25 are isostructural and isomorphous two-dimensional structures. The entire series was characterized by IR spectroscopy, thermogravimetric analysis, single-crystal X-ray diffraction and emission measurements. 2D coordination polymers accommodate water and dmf molecules in their cage-shaped interlayer spaces, which are released when the samples are heated. Thus, three solvated crystals were degassed at two temperatures and their photoluminescent and adsorption–desorption properties were recorded in order to validate this assumption. Solvent-free samples reveal an increase in volume pore, adsorption specific surface area and photoluminescence with regard to synthesized crystals. Full article
(This article belongs to the Special Issue Zn(II) and Cd(II) Coordination Polymers: Advances and Perspectives)
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20 pages, 7620 KiB  
Article
From 1D to 2D Cd(II) and Zn(II) Coordination Networks by Replacing Monocarboxylate with Dicarboxylates in Partnership with Azine Ligands: Synthesis, Crystal Structures, Inclusion, and Emission Properties
by Victor Ch. Kravtsov, Vasile Lozovan, Nikita Siminel, Eduard B. Coropceanu, Olga V. Kulikova, Natalia V. Costriucova and Marina S. Fonari
Molecules 2020, 25(23), 5616; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25235616 - 29 Nov 2020
Cited by 8 | Viewed by 1874
Abstract
Eight mixed-ligand coordination networks, [Cd(2-aba)(NO3)(4-bphz)3/2]n·n(dmf) (1), [Cd(2-aba)2(4-bphz)]n·0.75n(dmf) (2), [Cd(seb)(4-bphz)]n·n(H2O) (3), [Cd(seb)(4-bpmhz)]n·n(H2O) (4), [Cd(hpa)(3-bphz)]n (5), [...] Read more.
Eight mixed-ligand coordination networks, [Cd(2-aba)(NO3)(4-bphz)3/2]n·n(dmf) (1), [Cd(2-aba)2(4-bphz)]n·0.75n(dmf) (2), [Cd(seb)(4-bphz)]n·n(H2O) (3), [Cd(seb)(4-bpmhz)]n·n(H2O) (4), [Cd(hpa)(3-bphz)]n (5), [Zn(1,3-bdc)(3-bpmhz)]n·n(MeOH) (6), [Cd(1,3-bdc)(3-bpmhz)]n ·0.5n(H2O)·0.5n(EtOH) (7), and [Cd(NO3)2(3-bphz)(bpe)]n·n(3-bphz) (8) were obtained by interplay of cadmium nitrate tetrahydrate or zinc nitrate hexahydrate with 2-aminobenzenecarboxylic acid (H(2-aba)), three dicarboxylic acids, sebacic (decanedioic acid, H2seb), homophthalic (2-(carboxymethyl)benzoic acid, H2hpa), isophthalic (1,3-benzenedicarboxylic acid, H2(1,3-bdc)) acids, bis(4-pyridyl)ethane (bpe) and with four azine ligands, 1,2-bis(pyridin-4-ylmethylene)hydrazine (4-bphz), 1,2-bis(1-(pyridin-4-yl)ethylidene) hydrazine (4-bpmhz), 1,2-bis(pyridin-3-ylmethylene)hydrazine (3-bphz), and 1,2-bis(1-(pyridin-3-yl) ethylidene)hydrazine (3-bpmhz). Compounds 1 and 2 are 1D coordination polymers, while compounds 38 are 2D coordination polymers. All compounds were characterized by spectroscopic and X-ray diffraction methods of analysis. The solvent uptakes and stabilities to the guest evacuation were studied and compared for 1D and 2D coordination networks. The de-solvated forms revealed a significant increase of emission in comparison with the as-synthesized crystals. Full article
(This article belongs to the Special Issue Zn(II) and Cd(II) Coordination Polymers: Advances and Perspectives)
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12 pages, 4743 KiB  
Article
A Selenophene-Incorporated Metal–Organic Framework for Enhanced CO2 Uptake and Adsorption Selectivity
by Pavel A. Demakov, Sergey S. Volynkin, Denis G. Samsonenko, Vladimir P. Fedin and Danil N. Dybtsev
Molecules 2020, 25(19), 4396; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25194396 - 24 Sep 2020
Cited by 15 | Viewed by 2599
Abstract
A new metal–organic coordination polymer [Zn2(sedc)2(dabco)] (1se; sedc2− = selepophene-2,5-dicarboxylate; dabco = 1,4-diazabicyclo[2.2.2]octane) was synthesized and characterized by single-crystal X-ray diffraction analysis. This MOF is based on {Zn2(OOCR)4N2} paddle wheels [...] Read more.
A new metal–organic coordination polymer [Zn2(sedc)2(dabco)] (1se; sedc2− = selepophene-2,5-dicarboxylate; dabco = 1,4-diazabicyclo[2.2.2]octane) was synthesized and characterized by single-crystal X-ray diffraction analysis. This MOF is based on {Zn2(OOCR)4N2} paddle wheels and is isoreticular to the family of [Zn2(bdc)2(dabco)] derivatives (1b; bdc2− = 1,4-benzenedicarboxylate) with pcu topology. The gas adsorption measurements revealed that 1se shows a 15% higher CO2 volumetric uptake at 273 K and 28% higher CO2 uptake at 298 K (both at 1 bar) compared to the prototypic framework 1b. Methane and nitrogen adsorption at 273 K was also investigated, and IAST calculations demonstrated a pronounced increase in CO2/CH4 and CO2/N2 selectivity for 1se, compared with 1b. For example, the selectivity factor for the equimolar CO2/CH4 gas mixture at 1 bar = 15.1 for 1se and 11.9 for 1b. The obtained results show a remarkable effect of the presence of selenium atom on the carbon dioxide affinity in the isoreticular metal–organic frameworks with very similar geometry and porosity. Full article
(This article belongs to the Special Issue Zn(II) and Cd(II) Coordination Polymers: Advances and Perspectives)
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Review

Jump to: Research

30 pages, 2319 KiB  
Review
Zinc(II) Carboxylate Coordination Polymers with Versatile Applications
by Gina Vasile Scaeteanu, Catalin Maxim, Mihaela Badea and Rodica Olar
Molecules 2023, 28(3), 1132; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules28031132 - 23 Jan 2023
Cited by 6 | Viewed by 2958
Abstract
This review considers the applications of Zn(II) carboxylate-based coordination polymers (Zn-CBCPs), such as sensors, catalysts, species with potential in infections and cancers treatment, as well as storage and drug-carrier materials. The nature of organic luminophores, especially both the rigid carboxylate and the ancillary [...] Read more.
This review considers the applications of Zn(II) carboxylate-based coordination polymers (Zn-CBCPs), such as sensors, catalysts, species with potential in infections and cancers treatment, as well as storage and drug-carrier materials. The nature of organic luminophores, especially both the rigid carboxylate and the ancillary N-donor bridging ligand, together with the alignment in Zn-CBCPs and their intermolecular interaction modulate the luminescence properties and allow the sensing of a variety of inorganic and organic pollutants. The ability of Zn(II) to act as a good Lewis acid allowed the involvement of Zn-CBCPs either in dye elimination from wastewater through photocatalysis or in pathogenic microorganism or tumor inhibition. In addition, the pores developed inside of the network provided the possibility for some species to store gaseous or liquid molecules, as well as to deliver some drugs for improved treatment. Full article
(This article belongs to the Special Issue Zn(II) and Cd(II) Coordination Polymers: Advances and Perspectives)
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47 pages, 22673 KiB  
Review
Isomers of Terpyridine as Ligands in Coordination Polymers and Networks Containing Zinc(II) and Cadmium(II)
by Catherine E. Housecroft and Edwin C. Constable
Molecules 2021, 26(11), 3110; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26113110 - 23 May 2021
Cited by 12 | Viewed by 2787
Abstract
The use of divergent 4,2′:6′,4″- and 3,2′:6′,3″-terpyridine ligands as linkers and/or nodes in extended coordination assemblies has gained in popularity over the last decade. However, there is also a range of coordination polymers which feature 2,2′:6′,2″-terpyridine metal-binding domains. Of the remaining 45 isomers [...] Read more.
The use of divergent 4,2′:6′,4″- and 3,2′:6′,3″-terpyridine ligands as linkers and/or nodes in extended coordination assemblies has gained in popularity over the last decade. However, there is also a range of coordination polymers which feature 2,2′:6′,2″-terpyridine metal-binding domains. Of the remaining 45 isomers of terpyridine, few have been utilized in extended coordination arrays. Here, we provide an overview of coordination polymers and networks containing isomers of terpyridine and either zinc(II) and cadmium(II). Although the motivation for investigations of many of these systems is their luminescent behavior, we have chosen to focus mainly on structural details, and we assess to what extent assemblies are reproducible. We also consider cases where there is structural evidence for competitive product formation. A point that emerges is the lack of systematic investigations. Full article
(This article belongs to the Special Issue Zn(II) and Cd(II) Coordination Polymers: Advances and Perspectives)
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