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Molecule-Based Crystalline Materials
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Molecule-Based Crystalline Materials

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

Deadline for manuscript submissions: closed (30 April 2023) | Viewed by 13556

Special Issue Editor

Prof. Dr. Zhi-Gang Gu

E-Mail Website
Guest Editor
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
Interests: metal-organic framework; covalent organic framework; film; membrane; nonlinear optics; optical limiting; chirality; circularly polarized luminescence
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Molecule-based crystalline materials, including metal–organic frameworks (MOFs), covalent–organic frameworks (COFs), and supramolecular organic frameworks (SOFs), possess a highly specific surface area, well-defined and ordered pores, variable structures, and tunable chemical functionalities, attracting great attention for their potential applications in molecule adsorption and separation, photo/electrocatalysts, biomedical engineering and optical/electric devices and sensors, and so on. This Special Issue aims to provide an overview of recent discoveries of the synthesis and functions of molecule-based crystalline materials, including new designs of MOFs, COFs, SOFs, and other molecule-based complexes, the study of their growth mechanics, and their potential applications in a broad range of fields.

Prof. Dr. Zhi-Gang Gu
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

  • metal–organic frameworks
  • covalent–organic frameworks
  • supramolecular organic frameworks
  • crystalline materials
  • chemical synthesis
  • functional applications

Related Special Issue

Published Papers (7 papers)

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Research

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13 pages, 2642 KiB  
Article
Enhancing Third-Order Nonlinear Optical Property by Regulating Interaction between Zr4(embonate)6 Cage and N, N-Chelated Transition-Metal Cation
by Gang Xiang, Na Li, Guang-Hui Chen, Qiao-Hong Li, Shu-Mei Chen, Yan-Ping He and Jian Zhang
Molecules 2023, 28(5), 2301; https://doi.org/10.3390/molecules28052301 - 01 Mar 2023
Viewed by 1254
Abstract
Herein, the combination of anionic Zr4L6 (L = embonate) cages and N, N-chelated transition-metal cations leads to a series of new cage-based architectures, including ion pair structures (PTC-355 and PTC-356), dimer (PTC-357), and 3D frameworks ( [...] Read more.
Herein, the combination of anionic Zr4L6 (L = embonate) cages and N, N-chelated transition-metal cations leads to a series of new cage-based architectures, including ion pair structures (PTC-355 and PTC-356), dimer (PTC-357), and 3D frameworks (PTC-358 and PTC-359). Structural analyses show that PTC-358 exhibits a 2-fold interpenetrating framework with a 3,4-connected topology, and PTC-359 shows a 2-fold interpenetrating framework with a 4-connected dia network. Both PTC-358 and PTC-359 can be stable in air and other common solvents at room temperature. The investigations of third-order nonlinear optical (NLO) properties indicate that these materials show different degrees of optical limiting effects. It is surprising that increasing coordination interactions between anion and cation moieties can effectively enhance their third-order NLO properties, which can be attributed to the formation of coordination bonds that facilitate charge transfer. In addition, the phase purity, UV-vis spectra, and photocurrent properties of these materials were also studied. This work provides new ideas for the construction of third-order NLO materials. Full article
(This article belongs to the Special Issue Molecule-Based Crystalline Materials)
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8 pages, 2270 KiB  
Article
Reversible Regulation of Polar Gas Molecules by Azobenzene-Based Photoswitchable Metal–Organic Framework Thin Films
by Xuan Chen, Siyu Fang, Ping Xue, Jiming Huang, Mi Tang and Zhengbang Wang
Molecules 2023, 28(2), 877; https://doi.org/10.3390/molecules28020877 - 15 Jan 2023
Cited by 4 | Viewed by 1527
Abstract
The development of tunable molecule separation membranes requires materials with remote controllability and ultra-high separation capability. In this paper, a novel photoswitchable metal organic framework (MOF) thin film (Cu2(AzoBPDC)2) was prepared by liquid phase epitaxial layer-by-layer assembly to realize [...] Read more.
The development of tunable molecule separation membranes requires materials with remote controllability and ultra-high separation capability. In this paper, a novel photoswitchable metal organic framework (MOF) thin film (Cu2(AzoBPDC)2) was prepared by liquid phase epitaxial layer-by-layer assembly to realize the reversible remote-controlled switching. The azobenzene side groups in the Cu2(AzoBPDC)2 thin film showed excellent reversible photoswitching performance under UV (365 nm) and Vis (450 nm) irradiation, achieving the remote-controlled mode of the diffusion flux of polar gas molecules in the MOF thin film. Full article
(This article belongs to the Special Issue Molecule-Based Crystalline Materials)
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12 pages, 2467 KiB  
Article
X-H Bond Insertion Promoted by Heterogeneous Dirhodium Metal–Organic Cage with Alkynes as Safe Carbene Precursors
by Lianfen Chen, Chaoyi Zhao, Weixian Mo, Chunsheng Li and Xiaoming Lin
Molecules 2023, 28(2), 608; https://doi.org/10.3390/molecules28020608 - 06 Jan 2023
Cited by 2 | Viewed by 1181
Abstract
A facile and efficient methodology for the generation of the C-X (X = Si, B) bond through a carbene insertion process was demonstrated using a dirhodium metal–organic cage, MOC-Rh-1, as a heterogeneous catalyst. A series of functionalized alkynes were utilized as [...] Read more.
A facile and efficient methodology for the generation of the C-X (X = Si, B) bond through a carbene insertion process was demonstrated using a dirhodium metal–organic cage, MOC-Rh-1, as a heterogeneous catalyst. A series of functionalized alkynes were utilized as safe carbene precursors to furnish Si-H and B-H insertion products in moderate to excellent yields. These reactions featured a high atom-economy, a broad substrate scope, and mild reaction conditions. Moreover, the as-prepared MOC-Rh-1 catalyst was recovered easily from the reaction system by simple centrifugation and reused for ten runs without a significant loss in activity, which made good use of the valuable precious metal rhodium. Full article
(This article belongs to the Special Issue Molecule-Based Crystalline Materials)
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15 pages, 6131 KiB  
Article
A Double-Layer Hydrogel Dressing with High Mechanical Strength and Water Resistance Used for Drug Delivery
by Fangzhe Liu, Zihan Wang, Hui Guo, Haichao Li, Yulan Chen and Shuang Guan
Molecules 2023, 28(2), 499; https://doi.org/10.3390/molecules28020499 - 04 Jan 2023
Cited by 6 | Viewed by 1808
Abstract
Hydrogel dressings provide a moist wound healing environment, absorb the exudates of the wound, and have better biocompatibility than traditional dressings. However, it is still difficult to meet the needs of modern medicine due to the defects in drug burst release, weak mechanical [...] Read more.
Hydrogel dressings provide a moist wound healing environment, absorb the exudates of the wound, and have better biocompatibility than traditional dressings. However, it is still difficult to meet the needs of modern medicine due to the defects in drug burst release, weak mechanical strength, and poor water retention. To solve these problems, we developed a double-layer (DL) hydrogel based on β-cyclodextrin polymer (β-CDP), poly(vinyl alcohol) (PVA), and carboxymethyl cellulose sodium (CMC) via a layer-by-layer method. Inspired by natural coconut, this hydrogel consisted of a drug release layer (DRL) and a mechanical support layer (MSL). In our design, the introduction of β-CDP into the DRL slowed the drug release rate of the DL hydrogel. Furthermore, the mechanical strength of the hydrogel was improved by immersing the MSL in a calcium chloride/boric acid solution. Combining these two layers, the tensile strength and elongation at break of the DL hydrogel reached 1504 kPa and 400%, respectively. More interestingly, the release mechanism of DL hydrogel conformed to the diffusion–relaxation–erosion model, which was different from traditional hydrogel dressings. Therefore, the as-prepared DL structure represents a feasible solution for fabricating high-performance mechanical hydrogel dressings with sustained drug release properties, and the DL hydrogel has potential to be used for medical dressings applied in daily life. Full article
(This article belongs to the Special Issue Molecule-Based Crystalline Materials)
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15 pages, 4432 KiB  
Article
Ti3C2Tx-Modified PEDOT:PSS Hole-Transport Layer for Inverted Perovskite Solar Cells
by Israt Ali, Muhammad Faraz Ud Din, Daniele T. Cuzzupè, Azhar Fakharuddin, Hitler Louis, Ghulam Nabi and Zhi-Gang Gu
Molecules 2022, 27(21), 7452; https://doi.org/10.3390/molecules27217452 - 02 Nov 2022
Cited by 7 | Viewed by 2306
Abstract
PEDOT:PSS is a commonly used hole-transport layer (HTL) in inverted perovskite solar cells (PSCs) due to its compatibility with low-temperature solution processing. However, it possesses lower conductivity than other conductive polymers and metal oxides, along with surface defects, limiting its photovoltaic performance. In [...] Read more.
PEDOT:PSS is a commonly used hole-transport layer (HTL) in inverted perovskite solar cells (PSCs) due to its compatibility with low-temperature solution processing. However, it possesses lower conductivity than other conductive polymers and metal oxides, along with surface defects, limiting its photovoltaic performance. In this study, we introduced two-dimensional Ti3C2Tx (MXene) as an additive in the PEDOT:PSS HTL with varying doping concentrations (i.e., 0, 0.03, 0.05, and 0.1 wt.%) to tune the electrical conductivity of PEDOT:PSS and to modify the properties of the perovskite film atop it. We noted that the grain size of the CH3NH3PbI3 (MAPI3) perovskite layer grown over an optimal concentration of MXene (0.03 wt.%)-doped PEDOT:PSS increased from 250 nm to 400 nm, reducing charge recombination due to fewer grain boundaries. Ultraviolet photoelectron spectroscopy (UPS) revealed increased work function (WF) from 4.43 eV to 4.99 eV with 0.03 wt.% MXene doping, making the extraction of holes easier due to a more favorable energy level alignment with the perovskite. Quantum chemical investigations based on density functional theory (DFT) were conducted at the ωB97XD/6-311++G(d,p) level of theory to provide more insight into the stability, bonding nature, and optoelectronic properties of the PEDOT:PSS–MXene system. The theoretical investigations revealed that the doping of PEDOT:PSS with Ti3C2Tx could cause a significant effect on the electronic properties of the HTL, as experimentally demonstrated by an increase in the electrical conductivity. Finally, the inverted PSCs employing 0.03 wt.% MXene-doped PEDOT:PSS showed an average power conversion efficiency (PCE) of 15.1%, up from 12.5% for a reference PSC employing a pristine PEDOT:PSS HTL. The champion device with a 0.03 wt.% MXene–PEDOT:PSS HTL achieved 15.5% PCE. Full article
(This article belongs to the Special Issue Molecule-Based Crystalline Materials)
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Review

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53 pages, 27373 KiB  
Review
Recent Advances in Stimuli-Responsive Metallogels
by Zhixiong Liu, Xiaofang Zhao, Qingkai Chu and Yu Feng
Molecules 2023, 28(5), 2274; https://doi.org/10.3390/molecules28052274 - 28 Feb 2023
Cited by 15 | Viewed by 1908
Abstract
Recently, stimuli-responsive supramolecular gels have received significant attention because their properties can be modulated through external stimuli such as heat, light, electricity, magnetic fields, mechanical stress, pH, ions, chemicals and enzymes. Among these gels, stimuli-responsive supramolecular metallogels have shown promising applications in material [...] Read more.
Recently, stimuli-responsive supramolecular gels have received significant attention because their properties can be modulated through external stimuli such as heat, light, electricity, magnetic fields, mechanical stress, pH, ions, chemicals and enzymes. Among these gels, stimuli-responsive supramolecular metallogels have shown promising applications in material science because of their fascinating redox, optical, electronic and magnetic properties. In this review, research progress on stimuli-responsive supramolecular metallogels in recent years is systematically summarized. According to external stimulus sources, stimuli-responsive supramolecular metallogels, including chemical, physical and multiple stimuli-responsive metallogels, are discussed separately. Moreover, challenges, suggestions and opportunities regarding the development of novel stimuli-responsive metallogels are presented. We believe the knowledge and inspiration gained from this review will deepen the current understanding of stimuli-responsive smart metallogels and encourage more scientists to provide valuable contributions to this topic in the coming decades. Full article
(This article belongs to the Special Issue Molecule-Based Crystalline Materials)
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Graphical abstract

25 pages, 9286 KiB  
Review
Molecular Iodine Capture by Covalent Organic Frameworks
by Yuting Yang, Changzheng Tu, Hongju Yin, Jianjun Liu, Feixiang Cheng and Feng Luo
Molecules 2022, 27(24), 9045; https://doi.org/10.3390/molecules27249045 - 19 Dec 2022
Cited by 16 | Viewed by 3094
Abstract
The effective capture and storage of volatile molecular iodine from nuclear waste is of great significance. Covalent organic frameworks (COFs) are a class of extended crystalline porous polymers that possess unique architectures with high surface areas, long-range order, and permanent porosity. Substantial efforts [...] Read more.
The effective capture and storage of volatile molecular iodine from nuclear waste is of great significance. Covalent organic frameworks (COFs) are a class of extended crystalline porous polymers that possess unique architectures with high surface areas, long-range order, and permanent porosity. Substantial efforts have been devoted to the design and synthesis of COF materials for the capture of radioactive iodine. In this review, we first introduce research techniques for determining the mechanism of iodine capture by COF materials. Then, the influencing factors of iodine capture performance are classified, and the design principles and strategies for constructing COFs with potential for iodine capture are summarized on this basis. Finally, our personal insights on remaining challenges and future trends are outlined, in order to bring more inspiration to this hot topic of research. Full article
(This article belongs to the Special Issue Molecule-Based Crystalline Materials)
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