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Advances in Optical Functional Metal-Organic Complexes, Metal-Organic Frameworks (MOFs), Covalent Organic Frameworks (COFs) and Coordination Polymers

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

Deadline for manuscript submissions: closed (31 March 2022) | Viewed by 17283

Special Issue Editors

Dr. Boiko Cohen

E-Mail Website
Guest Editor
Departamento de Química Física, Facultad de Ciencias Ambientales y Bioquímica, and INAMOL, Universidad de Castilla-La Mancha, Avenida Carlos III, S/N, 45071 Toledo, Spain
Interests: photophysics; optical spectroscopy; femtochemistry; single molecule microscopy; ultrafast dynamics; confinement effect
Special Issues, Collections and Topics in MDPI journals
Dr. Mario Gutiérrez

E-Mail Website
Guest Editor
Departamento de Química Física, Facultad de Ciencias Ambientales y Bioquímica, and INAMOL, Universidad de Castilla-La Mancha, Avenida Carlos III, S/N, 45071 Toledo, Spain
Interests: luminescent MOFs; optical spectroscopy; femtochemistry; energy transfer; LMOF-sensors; LMOF-LEDs

Special Issue Information

Dear Colleagues,

Metal-organic frameworks (MOFs), coordination polymers and covalent organic frameworks (COFs) are porous crystalline materials that have attracted much attention in the field of gas storage/separation, catalysts, energy storage, and chemical sensors due to their highly porous structures. Of great interest for their potential application in photonic devices is the possibility to modulate their photoluminescence properties. These are often combined with guest molecules to form scaffolds with an improved response to external light stimuli. This could pave the way for an almost infinite branch of sensing applications, smart molecular-based detectors, and LEDs.

 

This Special Issue “Advances in Optical Functional Metal-Organic Complexes, Metal-Organic Frameworks (MOFs), Covalent Organic Frameworks (COFs) and Coordination Polymers” covers the design, preparation, characterization, and applications of novel luminescent metal-organic complexes, metal-organic frameworks, covalent organic frameworks, and luminescent coordination polymers. We cordially invite investigators to contribute original research and review articles that will stimulate further research activities in this area and improve our understanding of the key scientific and technological issues in the applications of luminescent metal-organic frameworks. We are particularly interested in articles describing new strategies for the synthesis, assembly, and modification of optical performance. Full papers, short communications, and review articles presenting and discussing the most recent trends in the field are welcome.


Dr. Boiko Cohen
Dr. Mario Gutiérrez
Guest Editors

Manuscript Submission Information

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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

  • luminescent MOFs
  • luminescent COFs
  • photofunctional coordination polymers
  • luminescent metal-organic complexes
  • luminescent metal-organic clusters
  • phototunable MOFs
  • sensors
  • LEDs

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Published Papers (5 papers)

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Research

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20 pages, 8631 KiB  
Article
pH-Responsive N^C-Cyclometalated Iridium(III) Complexes: Synthesis, Photophysical Properties, Computational Results, and Bioimaging Application
by Anastasia I. Solomatina, Daria O. Kozina, Vitaly V. Porsev and Sergey P. Tunik
Molecules 2022, 27(1), 232; https://doi.org/10.3390/molecules27010232 - 30 Dec 2021
Cited by 8 | Viewed by 2809
Abstract
Herein we report four [Ir(N^C)2(L^L)]n+, n = 0,1 complexes (1–4) containing cyclometallated N^C ligand (N^CH = 1-phenyl-2-(4-(pyridin-2-yl)phenyl)-1H-phenanthro[9,10-d]imidazole) and various bidentate L^L ligands (picolinic acid (1), 2,2′-bipyridine [...] Read more.
Herein we report four [Ir(N^C)2(L^L)]n+, n = 0,1 complexes (1–4) containing cyclometallated N^C ligand (N^CH = 1-phenyl-2-(4-(pyridin-2-yl)phenyl)-1H-phenanthro[9,10-d]imidazole) and various bidentate L^L ligands (picolinic acid (1), 2,2′-bipyridine (2), [2,2′-bipyridine]-4,4′-dicarboxylic acid (3), and sodium 4,4′,4″,4‴-(1,2-phenylenebis(phosphanetriyl))tetrabenzenesulfonate (4). The N^CH ligand precursor and iridium complexes 1–4 were synthesized in good yield and characterized using chemical analysis, ESI mass spectrometry, and NMR spectroscopy. The solid-state structure of 2 was also determined by XRD analysis. The complexes display moderate to strong phosphorescence in the 550–670 nm range with the quantum yields up to 30% and lifetimes of the excited state up to 60 µs in deoxygenated solution. Emission properties of 1–4 and N^CH are strongly pH-dependent to give considerable variations in excitation and emission profiles accompanied by changes in emission efficiency and dynamics of the excited state. Density functional theory (DFT) and time-dependent density functional theory (TD DFT) calculations made it possible to assign the nature of emissive excited states in both deprotonated and protonated forms of these molecules. The complexes 3 and 4 internalize into living CHO-K1 cells, localize in cytoplasmic vesicles, primarily in lysosomes and acidified endosomes, and demonstrate relatively low toxicity, showing more than 80% cells viability up to the concentration of 10 µM after 24 h incubation. Phosphorescence lifetime imaging microscopy (PLIM) experiments in these cells display lifetime distribution, the conversion of which into pH values using calibration curves gives the magnitudes of this parameter compatible with the physiologically relevant interval of the cell compartments pH. Full article
(This article belongs to the Special Issue Advances in Optical Functional Metal-Organic Complexes, Metal-Organic Frameworks (MOFs), Covalent Organic Frameworks (COFs) and Coordination Polymers)
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10 pages, 2626 KiB  
Article
A Luminescent Guest@MOF Nanoconfined Composite System for Solid-State Lighting
by Tao Xiong, Yang Zhang, Nader Amin and Jin-Chong Tan
Molecules 2021, 26(24), 7583; https://doi.org/10.3390/molecules26247583 - 14 Dec 2021
Cited by 9 | Viewed by 3184
Abstract
A series of rhodamine B (RhB) encapsulated zeolitic imidazolate framework-8 (RhB@ZIF-8) composite nanomaterials with different concentrations of guest loadings have been synthesized and characterized in order to investigate their applicability to solid-state white-light-emitting diodes (WLEDs). The nanoconfinement of the rhodamine B dye (guest) [...] Read more.
A series of rhodamine B (RhB) encapsulated zeolitic imidazolate framework-8 (RhB@ZIF-8) composite nanomaterials with different concentrations of guest loadings have been synthesized and characterized in order to investigate their applicability to solid-state white-light-emitting diodes (WLEDs). The nanoconfinement of the rhodamine B dye (guest) in the sodalite cages of ZIF-8 (host) is supported by fluorescence spectroscopic and photodynamic lifetime data. The quantum yield (QY) of the luminescent RhB@ZIF-8 material approaches unity when the guest loading is controlled at a low level: 1 RhB guest per ~7250 cages. We show that the hybrid (luminescent guest) LG@MOF material, obtained by mechanically mixing a suitably high-QY RhB@ZIF-8 red emitter with a green-emitting fluorescein@ZIF-8 “phosphor” with a comparably high QY, could yield a stable, intensity tunable, near-white light emission under specific test conditions described. Our results demonstrate a novel LG@MOF composite system exhibiting a good combination of photophysical properties and photostability, for potential applications in WLEDs, photoswitches, bioimaging and fluorescent sensors. Full article
(This article belongs to the Special Issue Advances in Optical Functional Metal-Organic Complexes, Metal-Organic Frameworks (MOFs), Covalent Organic Frameworks (COFs) and Coordination Polymers)
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12 pages, 3153 KiB  
Article
A Zn(II)-Based Sql Type 2D Coordination Polymer as a Highly Sensitive and Selective Turn-On Fluorescent Probe for Al3+
by Dmitry I. Pavlov, Alexey A. Ryadun and Andrei S. Potapov
Molecules 2021, 26(23), 7392; https://doi.org/10.3390/molecules26237392 - 6 Dec 2021
Cited by 8 | Viewed by 2485
Abstract
A luminescent coordination polymer with the overall formula {[Zn(tr2btd)(bpdc)]∙DMF}n (where tr2btd = 4,7-di(1H-1,2,4-triazol-1-yl)-2,1,3-benzothiadiazole; bpdc = 4,4′-biphenyldicarboxylate) was synthesized and characterized by single-crystal and powder X-ray diffraction, thermogravimetric, infrared spectroscopy, and elemental analyses. Luminescent properties of the [...] Read more.
A luminescent coordination polymer with the overall formula {[Zn(tr2btd)(bpdc)]∙DMF}n (where tr2btd = 4,7-di(1H-1,2,4-triazol-1-yl)-2,1,3-benzothiadiazole; bpdc = 4,4′-biphenyldicarboxylate) was synthesized and characterized by single-crystal and powder X-ray diffraction, thermogravimetric, infrared spectroscopy, and elemental analyses. Luminescent properties of the obtained compound were studied in detail both in the solid state and as a suspension in N,N-dimethylacetamide (DMA). It was found that {[Zn(tr2btd)(bpdc)]∙DMF}n exhibits bright turquoise luminescence with excellent quantum efficiency and demonstrates turn-on fluorescence enhancement effect upon soaking in DMA Al3+ solution. Fluorescence titration experiments were carried out and the detection limit for Al3+ ions was calculated to be 120 nM, which is among the lowest reported values for similar materials. Moreover, compound demonstrated excellent selectivity and reusability, and the mechanism of the response is discussed. These results indicate that {[Zn(tr2btd)(bpdc)]∙DMF}n is a promising probe for sensitive fluorescent Al3+ detection. Full article
(This article belongs to the Special Issue Advances in Optical Functional Metal-Organic Complexes, Metal-Organic Frameworks (MOFs), Covalent Organic Frameworks (COFs) and Coordination Polymers)
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18 pages, 8581 KiB  
Article
Construction of Two Stable Co(II)-Based Hydrogen-Bonded Organic Frameworks as a Luminescent Probe for Recognition of Fe3+ and Cr2O72− in H2O
by Qi-Ying Weng, Ya-Li Zhao, Jia-Ming Li and Miao Ouyang
Molecules 2021, 26(19), 5955; https://doi.org/10.3390/molecules26195955 - 30 Sep 2021
Cited by 7 | Viewed by 2159
Abstract
A pair of cobalt(II)-based hydrogen-bonded organic frameworks (HOFs), [Co(pca)2(bmimb)]n (1) and [Co2(pca)4(bimb)2] (2), where Hpca = p-chlorobenzoic acid, bmimb = 1,3-bis((2-methylimidazol-1-yl)methyl)benzene, and bimb = 1,4-bis(imidazol-1-ylmethyl)benzene were hydrothermally synthesized and [...] Read more.
A pair of cobalt(II)-based hydrogen-bonded organic frameworks (HOFs), [Co(pca)2(bmimb)]n (1) and [Co2(pca)4(bimb)2] (2), where Hpca = p-chlorobenzoic acid, bmimb = 1,3-bis((2-methylimidazol-1-yl)methyl)benzene, and bimb = 1,4-bis(imidazol-1-ylmethyl)benzene were hydrothermally synthesized and characterized through infrared spectroscopy (IR), elemental and thermal analysis (EA), power X-ray diffraction (PXRD), and single-crystal X-ray diffraction (SCXRD) analyses. X-ray diffraction structural analysis revealed that 1 has a one-dimensional (1D) infinite chain network through the deprotonated pca− monodentate chelation and with a μ2-bmimb bridge Co(II) atom, and 2 is a binuclear Co(II) complex construction with a pair of symmetry-related pca− and bimb ligands. For both 1 and 2, each cobalt atom has four coordinated twisted tetrahedral configurations with a N2O2 donor set. Then, 1 and 2 are further extended into three-dimensional (3D) or two-dimensional (2D) hydrogen-bonded organic frameworks through C–H···Cl interactions. Topologically, HOFs 1 and 2 can be simplified as a 4-connected qtz topology with a Schläfli symbol {64·82} and a 4-connected sql topology with a Schläfli symbol {44·62}, respectively. The fluorescent sensing application of 1 was investigated; 1 exhibits high sensitivity recognition for Fe3+ (Ksv: 10970 M−1 and detection limit: 19 μM) and Cr2O72− (Ksv: 12960 M−1 and detection limit: 20 μM). This work provides a feasible detection platform of HOFs for highly sensitive discrimination of Fe3+ and Cr2O72− in aqueous media. Full article
(This article belongs to the Special Issue Advances in Optical Functional Metal-Organic Complexes, Metal-Organic Frameworks (MOFs), Covalent Organic Frameworks (COFs) and Coordination Polymers)
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Review

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20 pages, 6021 KiB  
Review
Thiophene-Based Covalent Organic Frameworks: Synthesis, Photophysics and Light-Driven Applications
by Rubén Caballero, Boiko Cohen and Mario Gutiérrez
Molecules 2021, 26(24), 7666; https://doi.org/10.3390/molecules26247666 - 17 Dec 2021
Cited by 16 | Viewed by 5589
Abstract
Porous crystalline materials, such as covalent organic frameworks (COFs), have emerged as some of the most important materials over the last two decades due to their excellent physicochemical properties such as their large surface area and permanent, accessible porosity. On the other hand, [...] Read more.
Porous crystalline materials, such as covalent organic frameworks (COFs), have emerged as some of the most important materials over the last two decades due to their excellent physicochemical properties such as their large surface area and permanent, accessible porosity. On the other hand, thiophene derivatives are common versatile scaffolds in organic chemistry. Their outstanding electrical properties have boosted their use in different light-driven applications (photocatalysis, organic thin film transistors, photoelectrodes, organic photovoltaics, etc.), attracting much attention in the research community. Despite the great potential of both systems, porous COF materials based on thiophene monomers are scarce due to the inappropriate angle provided by the latter, which hinders its use as the building block of the former. To circumvent this drawback, researchers have engineered a number of thiophene derivatives that can form part of the COFs structure, while keeping their intrinsic properties. Hence, in the present minireview, we will disclose some of the most relevant thiophene-based COFs, highlighting their basic components (building units), spectroscopic properties and potential light-driven applications. Full article
(This article belongs to the Special Issue Advances in Optical Functional Metal-Organic Complexes, Metal-Organic Frameworks (MOFs), Covalent Organic Frameworks (COFs) and Coordination Polymers)
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