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1.
Yearin Byun Lilia S. Xie Patrick Fritz Timur Ashirov Mircea Dinc Ali Coskun 《Angewandte Chemie (International ed. in English)》2020,59(35):15166-15170
Dimensionality plays an important role in the charge transport properties of organic semiconductors. Although three‐dimensional semiconductors, such as Si, are common in inorganic materials, imparting electrical conductivity to covalent three‐dimensional organic polymers is challenging. Now, the synthesis of a three‐dimensional π‐conjugated porous organic polymer (3D p‐POP) using catalyst‐free Diels–Alder cycloaddition polymerization followed by acid‐promoted aromatization is presented. With a surface area of 801 m2 g?1, full conjugation throughout the carbon backbone, and an electrical conductivity of 6(2)×10?4 S cm?1 upon treatment with I2 vapor, the 3D p‐POP is the first member of a new class of permanently porous 3D organic semiconductors. 相似文献
2.
Water‐soluble three‐dimensional (3D) polymers are structurally ideal for the construction of ordered porous materials for in‐situ and tunable loading and release of guests. For many years, studies on ordered porous materials have been confined to crystalline solids. Since 2014, self‐assembly has been developed as a robust strategy for the preparation of water‐soluble 3D polymers that possess defined and intrinsic porosity. Through the encapsulation of cucurbit[8]uril for aromatic dimers, ordered diamondoid supramolecular organic frameworks can be assembled from tetrahedral monomers. With [Ru(bipy)3]2+‐derived octahedral complexes as precursors, cubic supramolecular metal‐organic frameworks have been assembled. One supramolecular organic framework has also been utilized to prepare the first homogeneous covalent organic framework through the [2+2] alkene cycloaddition, whereas the quantitative formation of the hydrazone bonds can be utilized to synthesize flexible porous organic frameworks. The new water‐soluble ordered and flexible polymeric frameworks are able to include drugs and biomacromolecules to accomplish in situ loading and intracellular delivery and to enrich photosensitizers and catalysts to enhance discrete visible light‐induced reactions. This review highlights the advances. 相似文献
3.
In‐Hyeok Park Anjana Chanthapally Dr. Zhenjie Zhang Prof. Dr. Shim Sung Lee Prof. Dr. Michael J. Zaworotko Prof. Dr. Jagadese J. Vittal 《Angewandte Chemie (International ed. in English)》2014,53(2):414-419
Organic polymers are usually amorphous or possess very low crystallinity. The metal complexes of organic polymeric ligands are also difficult to crystallize by traditional methods because of their poor solubilities and their 3D structures can not be determined by single‐crystal X‐ray crystallography owing to a lack of single crystals. Herein, we report the crystal structure of a 1D ZnII coordination polymer fused with an organic polymer ligand made in situ by a [2+2] cycloaddition reaction of a six‐fold interpenetrated metal–organic framework. It is also shown that this organic polymer ligand can be depolymerized in a single‐crystal‐to‐single‐crystal (SCSC) fashion by heating. This strategy could potentially be extended to make a range of monocrystalline metal organopolymeric complexes and metal–organic organopolymeric hybrid materials. Such monocrystalline metal complexes of organic polymers have hitherto been inaccessible for materials researchers. 相似文献
4.
Dipl.‐Chem. Andreas Kraft B. Sc. Patrick Roth Dr. David Schmidt M. Sc. Johannes Stangl Prof. Dr. Klaus Müller‐Buschbaum Dr. Florian Beuerle 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(17):5982-5987
Hexakis‐substituted [60]fullerene adducts with icosahedral symmetry provide an unprecedented scaffold for the spatial arrangement of twelve functional groups with high geometric precision. This unique molecular symmetry identifies such polyfunctional organic building blocks as potential highly connective linkers for coordination polymer and metal–organic framework synthesis. Hereby, the linker exhibits a higher connectivity than the metal ions and with the main connectivity based on the ligand, this can create a new type of inversely cross‐linked framework. Two hexakis adducts bearing either twelve glycolic acid or 3‐hydroxypropionic acid side chains attached to its malonate units were incorporated as organic connectivity centers in the first fullerene‐containing three‐dimensional frameworks by coordination with Zn2+. 相似文献
5.
Zhenzhen Yang Hao Chen Bo Li Wei Guo Kecheng Jie Yifan Sun De‐en Jiang Ilja Popovs Sheng Dai 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(39):13901-13905
Progress toward the preparation of porous organic polymers (POPs) with task‐specific functionalities has been exceedingly slow—especially where polymers containing low‐oxidation phosphorus in the structure are concerned. A two‐step topotactic pathway for the preparation of phosphabenzene‐based POPs (Phos‐POPs) under metal‐free conditions is reported, without the use of unstable phosphorus‐based monomers. The synthetic route allows additional functionalities to be introduced into the porous polymer framework with ease. As an example, partially fluorinated Phos‐POPs (F‐Phos‐POPs) were obtained with a surface area of up to 591 m2 g?1. After coordination with Ru species, a Ru/F‐Phos‐POPs catalyst exhibited high catalytic efficiency in the formylation of amines (turnover frequency up to 204 h?1) using a CO2/H2 mixture, in comparison with the non‐fluorinated analogue (43 h?1) and a Au/TiO2 heterogeneous catalysts reported previously (<44 h?1). This work describes a practical method for synthesis of porous organic phosphorus‐based polymers with applications in transition‐metal‐based heterogeneous catalysis. 相似文献
6.
Jelena Rogan Dejan Poleti Ljiljana Karanovi 《Acta Crystallographica. Section C, Structural Chemistry》2011,67(7):m230-m233
The novel title coordination polymer, {[Cu(C8H4O4)(C10H9N3)]·H2O}n, synthesized by the slow‐diffusion method, takes the form of one‐dimensional zigzag chains built up of CuII cations linked by benzene‐1,3‐dicarboxylate (ipht) anions. An exceptional characteristic of this structure is that it belongs to a small group of metal–organic polymers where ipht is coordinated as a bridging tridentate ligand with monodentate and chelate coordination of individual carboxylate groups. The CuII cation has a highly distorted square‐pyramidal geometry formed by three O atoms from two ipht anions and two N atoms from a di‐2‐pyridylamine (dipya) ligand. The zigzag chains, which run along the b axis, further construct a three‐dimensional metal–organic framework via strong face‐to‐face π–π interactions and hydrogen bonds. A solvent water molecule is linked to the different carboxylate groups via hydrogen bonds. Thermogravimetric and differential scanning calorimetric analyses confirm the strong hydrogen bonding. 相似文献
7.
Dr. Witold M. Bloch Prof. Neil R. Champness Prof. Christian J. Doonan 《Angewandte Chemie (International ed. in English)》2015,54(44):12860-12867
Open‐framework materials, such as metal–organic frameworks (MOFs) and coordination polymers have been widely investigated for their gas adsorption and separation properties. However, recent studies have demonstrated that their highly crystalline structures can be used to periodically organize guest molecules and non‐structural metal compounds either within their pore voids or by anchoring to their framework architecture. Accordingly, the open framework can act as a matrix for isolating and elucidating the structures of these moieties by X‐ray diffraction. This concept has broad scope for development as an analytical tool where obtaining single crystals of a target molecule presents a significant challenge and it additionally offers potential for obtaining insights into chemically reactive species that can be stabilized within the pore network. However, the technique does have limitations and as yet a general experimental method has not been realized. Herein we focus on recent examples in which framework materials have been utilized as a scaffold for ordering molecules for analysis by diffraction methods and canvass areas for future exploration. 相似文献
8.
《Angewandte Chemie (International ed. in English)》2017,56(32):9292-9310
Research into extended porous materials such as metal‐organic frameworks (MOFs) and porous organic frameworks (POFs), as well as the analogous metal‐organic polyhedra (MOPs) and porous organic cages (POCs), has blossomed over the last decade. Given their chemical and structural variability and notable porosity, MOFs have been proposed as adsorbents for industrial gas separations and also as promising filler components for high‐performance mixed‐matrix membranes (MMMs). Research in this area has focused on enhancing the chemical compatibility of the MOF and polymer phases by judiciously functionalizing the organic linkers of the MOF, modifying the MOF surface chemistry, and, more recently, exploring how particle size, morphology, and distribution enhance separation performance. Other filler materials, including POFs, MOPs, and POCs, are also being explored as additives for MMMs and have shown remarkable anti‐aging performance and excellent chemical compatibility with commercially available polymers. This Review briefly outlines the state‐of‐the‐art in MOF‐MMM fabrication, and the more recent use of POFs and molecular additives. 相似文献
9.
Chih‐Ping Chen Gwo‐Su Huang Ru‐Jong Jeng Che‐Chung Chou Wen‐Chiung Su Huey‐Ling Chang 《先进技术聚合物》2004,15(10):587-592
A series of crossslinked organic and organic/inorganic polymers based on maleimide chemistry have been investigated for second‐order non‐linear optical (NLO) materials with excellent thermal stability and low optical loss. Two reactive chromophores (maleimide‐containing azobenzene dye and alkoxysilane‐containing azobenzene dye) were incorporated into a phosphorus‐containing maleimide polymer, respectively. The selection of the phosphorus‐containing maleimide polymer as the polymeric matrices provides enhanced solubility and thermal stability, and excellent optical quality. Moreover, a full interpenetrating network (IPN) was formed through simultaneous addition reaction of the phosphorus‐containing maleimide, and sol‐gel process of alkoxysilane dye (ASD). Atomic force microscopy (AFM) results indicate that the inorganic networks are distributed uniformly throughout the polymer matrices on a nano‐scale. The silica particle sizes are well under 100 nm. Using in situ contact poling, the r33 coefficients of 2.2–17.0 pm/V have been obtained for the optically clear phosphorus‐containing NLO materials. Excellent temporal stability (100°C) and low optical loss (0.99–1.71 dB/cm; 830 nm) were also obtained for these phosphorus‐containing materials. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
10.
An Amide‐Functionalized Dynamic Metal–Organic Framework Exhibiting Visual Colorimetric Anion Exchange and Selective Uptake of Benzene over Cyclohexane 下载免费PDF全文
Avishek Karmakar Aamod V. Desai Biplab Manna Biplab Joarder Dr. Sujit K. Ghosh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(19):7071-7076
A novel porous metal–organic framework (MOF) architecture is formed by a neutral amide‐functionalized ligand and copper(II). Upon desolvation, this compound undergoes a dynamic structural transformation from a one‐dimensional (1D) porous phase to a two‐dimensional (2D) non‐porous phase that shows selective uptake of benzene over cyclohexane. The as‐synthesized compound also acts as a visual colorimetric anion sensor for thiocyanate. 相似文献
11.
Unusual Transformation from a Solvent‐Stabilized 1D Coordination Polymer to a Metal–Organic Framework (MOF)‐Like Cross‐Linked 3D Coordination Polymer 下载免费PDF全文
Seung‐Chul Lee Dr. Eun‐Young Choi Sang‐Beom Lee Prof. Dr. Sang‐Wook Kim Prof. Dr. O‐Pil Kwon 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(44):15570-15574
An unusual 1D‐to‐3D transformation of a coordination polymer based on organic linkers containing highly polar push–pull π‐conjugated side chains is reported. The coordination polymers are synthesized from zinc nitrate and an organic linker, namely, 2,5‐bis{4‐[1‐(4‐nitrophenyl)pyrrolidin‐2‐yl]butoxy}terephthalic acid, which possesses highly polar (4‐nitrophenyl)pyrrolidine groups, with high dipole moments of about 7 D. The coordination polymers exhibit an unusual transformation from a soluble, solvent‐stabilized 1D coordination polymer into an insoluble, metal–organic framework (MOF)‐like 3D coordination polymer. The coordination polymer exhibits good film‐forming ability, and the MOF‐like films are insoluble in conventional organic solvents. 相似文献
12.
Yan Wang Ying‐Zhong Shen 《Acta Crystallographica. Section C, Structural Chemistry》2008,64(8):m283-m285
The title novel heterometallic 3d–4f coordination polymer, {[CuEr2(C5HN2O4)2(C2O4)(H2O)6]·3H2O}n, has a three‐dimensional metal–organic framework composed of two types of metal atoms (one CuII and two ErIII) and two types of bridging anionic ligands [3,5‐dicarboxylatopyrazolate(3−) (ptc3−) and oxalate]. The CuII atom is four‐coordinated in a square geometry. The ErIII atoms are both eight‐coordinated, but the geometries at the two atoms appear different, viz. triangular dodecahedral and bicapped trigonal prismatic. One of the oxalate anions is located on a twofold axis and the other lies about an inversion centre. Both oxalate anions act as bis‐bidentate ligands bridging the latter type of Er atoms in parallel zigzag chains. The pdc3− anions act as quinquedentate ligands not only chelating the CuII and the triangular dodecahedral ErIII centres in a bis‐bidentate bridging mode, but also connecting to ErIII centres of both types in a monodentate bridging mode. Thus, a three‐dimensional metal–organic framework is generated, and hydrogen bonds link the metal–organic framework with the uncoordinated water molecules. This study describes the first example of a three‐dimensional 3d–4f coordination polymer based on pyrazole‐3,5‐dicarboxylate and oxalate, and therefore demonstrates further the usefulness of pyrazoledicarboxylate as a versatile multidentate ligand for constructing heterometallic 3d–4f coordination polymers with interesting architectures. 相似文献
13.
Avishek Karmakar Paulo G. M. Mileo Ivan Bok Shing Bo Peh Jian Zhang Hongye Yuan Guillaume Maurin Dan Zhao 《Angewandte Chemie (International ed. in English)》2020,59(27):11003-11009
We report an in situ polymerization strategy to incorporate a thermo‐responsive polymer, poly(N‐isopropylacrylamide) (PNIPAM), with controlled loadings into the cavity of a mesoporous metal–organic framework (MOF), MIL‐101(Cr). The resulting MOF/polymer composites exhibit an unprecedented temperature‐triggered water capture and release behavior originating from the thermo‐responsive phase transition of the PNIPAM component. This result sheds light on the development of stimuli‐responsive porous adsorbent materials for water capture and heat transfer applications under relatively mild operating conditions. 相似文献
14.
Hydrogen‐Bonded Organic Frameworks (HOFs): A New Class of Porous Crystalline Proton‐Conducting Materials 下载免费PDF全文
Avishek Karmakar Rajith Illathvalappil Bihag Anothumakkool Arunabha Sen Partha Samanta Aamod V. Desai Dr. Sreekumar Kurungot Dr. Sujit K. Ghosh 《Angewandte Chemie (International ed. in English)》2016,55(36):10667-10671
Two porous hydrogen‐bonded organic frameworks (HOFs) based on arene sulfonates and guanidinium ions are reported. As a result of the presence of ionic backbones appended with protonic source, the compounds exhibit ultra‐high proton conduction values (σ) 0.75× 10?2 S cm?1 and 1.8×10?2 S cm?1 under humidified conditions. Also, they have very low activation energy values and the highest proton conductivity at ambient conditions (low humidity and at moderate temperature) among porous crystalline materials, such as metal–organic frameworks (MOFs) and covalent organic frameworks (COFs). These values are not only comparable to the conventionally used proton exchange membranes, such as Nafion used in fuel cell technologies, but is also the highest value reported in organic‐based porous architectures. Notably, this report inaugurates the usage of crystalline hydrogen‐bonded porous organic frameworks as solid‐state proton conducting materials. 相似文献
15.
Pattiya Krinchampa Kittipong Chainok Siriporn Phengthaisong Sujittra Youngme Filip Kielar Nanthawat Wannarit 《Acta Crystallographica. Section C, Structural Chemistry》2016,72(12):960-965
One of most interesting systems of coordination polymers constructed from the first‐row transition metals is the porous ZnII coordination polymer system, but the numbers of such polymers containing N‐donor linkers are still limited. The title double‐chain‐like ZnII coordination polymer, [Ag2Zn(CN)4(C10H10N2)2]n, presents a one‐dimensional linear coordination polymer structure in which ZnII ions are linked by bridging anionic dicyanidoargentate(I) units along the crystallographic b axis and each ZnII ion is additionally coordinated by a terminal dicyanidoargentate(I) unit and two terminal 1‐benzyl‐1H‐imidazole (BZI) ligands, giving a five‐coordinated ZnII ion. Interestingly, there are strong intermolecular AgI…AgI interactions between terminal and bridging dicyanidoargentate(I) units and C—H…π interactions between the phenyl rings of BZI ligands of adjacent one‐dimensional linear chains, providing a one‐dimensional linear double‐chain‐like structure. The supramolecular three‐dimensional framework is stabilized by C—H…π interactions between the phenyl rings of BZI ligands and by AgI…AgI interactions between adjacent double chains. The photoluminescence properties have been studied. 相似文献
16.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(9):2453-2457
The solvent‐free mechanical milling process for two distinct metal–organic framework (MOF) crystals induced the formation of a solid solution, which is not feasible by conventional solution‐based syntheses. X‐ray and STEM‐EDX studies revealed that performing mechanical milling under an Ar atmosphere promotes the high diffusivity of each metal ion in an amorphous solid matrix; the amorphous state turns into the porous crystalline structure by vapor exposure treatment to form a new phase of a MOF solid solution. 相似文献
17.
Versatile Tailoring of Paddle‐Wheel ZnII Metal–Organic Frameworks through Single‐Crystal‐to‐Single‐Crystal Transformations 下载免费PDF全文
Tapan K. Pal Dr. Subhadip Neogi Prof. Parimal K. Bharadwaj 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(45):16083-16090
A new tetracarboxylate ligand having short and long arms formed 2D layer ZnII coordination polymer 1 with paddle‐wheel secondary building units under solvothermal conditions. The framework undergoes solvent‐specific single crystal‐to‐single crystal (SC‐SC) transmetalation to produce 1Cu . With a sterically encumbered dipyridyl linker, the same ligand forms non‐interpenetrated, 3D, pillared‐layer ZnII metal–organic framework (MOF) 2 , which takes part in SC‐SC linker‐exchange reactions to produce three daughter frameworks. The parent MOF 2 shows preferential incorporation of the longest linker in competitive linker‐exchange experiments. All the 3D MOFs undergo complete SC‐SC transmetalation with CuII, whereby metal exchange in different solvents and monitoring of X‐ray structures revealed that bulky solvated metal ions lead to ordering of the shortest linker in the framework, which confirms that the solvated metal ions enter through the pores along the linker axis. 相似文献
18.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2018,130(39):12832-12837
Enhancing thermal and chemical durability and increasing surface area are two main directions for the construction and improvement of the performance of porous hydrogen‐bonded organic frameworks (HOFs). Herein, a hexaazatriphenylene (HAT) derivative that possesses six carboxyaryl groups serves as a suitable building block for the systematic construction of thermally and chemically durable HOFs with high surface area through shape‐fitted docking between the HAT cores and interpenetrated three‐dimensional network. A HAT derivative with carboxybiphenyl groups forms a stable single‐crystalline porous HOF that displays protic solvent durability, even in concentrated HCl, heat resistance up to 305 °C, and a high Brunauer–Emmett–Teller surface area [SA(BET)] of 1288 m2 g−1. A single crystal of this HOF displays anisotropic fluorescence, which suggests that it would be applicable to polarized emitters based on robust functional porous materials. 相似文献
19.
Docking Strategy To Construct Thermostable,Single‐Crystalline,Hydrogen‐Bonded Organic Framework with High Surface Area 下载免费PDF全文
Dr. Ichiro Hisaki Yuto Suzuki Eduardo Gomez Dr. Boiko Cohen Dr. Norimitsu Tohnai Prof. Dr. Abderrazzak Douhal 《Angewandte Chemie (International ed. in English)》2018,57(39):12650-12655
Enhancing thermal and chemical durability and increasing surface area are two main directions for the construction and improvement of the performance of porous hydrogen‐bonded organic frameworks (HOFs). Herein, a hexaazatriphenylene (HAT) derivative that possesses six carboxyaryl groups serves as a suitable building block for the systematic construction of thermally and chemically durable HOFs with high surface area through shape‐fitted docking between the HAT cores and interpenetrated three‐dimensional network. A HAT derivative with carboxybiphenyl groups forms a stable single‐crystalline porous HOF that displays protic solvent durability, even in concentrated HCl, heat resistance up to 305 °C, and a high Brunauer–Emmett–Teller surface area [SA(BET)] of 1288 m2 g?1. A single crystal of this HOF displays anisotropic fluorescence, which suggests that it would be applicable to polarized emitters based on robust functional porous materials. 相似文献
20.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2018,130(19):5443-5447
Self‐assembled crystalline porous organic salts (CPOSs) formed by an acid–base combination and with one‐dimensional polar channels containing water molecules have been synthesized. The water content in the channels of the porous salts plays an important role in the proton conduction performance of the materials. The porous salts described in this study feature high proton conductivity at ambient conditions and can reach as high as 2.2×10−2 S cm−1 at 333 K and under high humid conditions. This is among the best conductivity values reported to date for porous materials, for example, metal–organic frameworks and hydrogen‐bonded organic frameworks. These materials exhibiting permanent porosity represent a group of porous materials and may find interesting applications in proton‐exchange membrane fuel cells. 相似文献