Tröger’s base-functionalised organic nanoporous polymer for heterogeneous catalysis

Du, Xin; Sun, Ya‐Lei; Tan, Bien; Teng, Qingfeng; Yao, Xiaojun; Su, Cheng‐Yong; Wang, Wei

doi:10.1039/b920113k

Cited by 222 publications

(136 citation statements)

References 25 publications

(20 reference statements)

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“…Recently, a few examples of CMPs showing catalytic activity have been reported. [10,17] Polymer C contains a cyclometalated Ir III complex which is closely related to a class of successful reductive amination catalysts. [18] We therefore examined the heterogeneous catalytic activity of the CMP-CpIr networks.…”

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confidence: 99%

Metal–Organic Conjugated Microporous Polymers

et al. 2010

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Microporous materials have potential applications in areas including molecular separation, gas sorption and catalysis. [1] Materials such as metal-organic frameworks (MOFs), [2] covalent organic frameworks (COFs), [3] microporous organic polymers, [4] and porous organic molecular solids [5] all contain organic functionalities which, in principle, can allow significant synthetic diversification. A particular advantage of microporous organic polymers [4] is the potential to introduce a range of useful chemical functionalities into the pores. [6] This stems from the chemical and thermal stability of these networks which facilitates a variety of chemical transformations.Conjugated microporous polymers (CMPs) [4a] can exhibit extended p-conjugation and have been the subject of much recent interest. A variety of CMPs (and closely related structures) have been developed. [4a, 7] The incorporation of metal sites into CMPs could open up second-generation porous materials with useful combined chemical and physical properties such as catalytic activity, electrical conductivity, or light-absorption/emission.[8] For example, metalated CMP materials might be of interest in heterogeneous catalysis or photocatalysis, where high surface areas would be beneficial. There are, however, few demonstrations of the functionalization of CMP networks with metals at the molecular level. The incorporation of metal nanoparticles into microporous networks has been demonstrated.[4e, 7e, 9a] Also, a lithiated CMP showing very high H 2 sorption was described recently but the precise nature of the metal incorporation at the molecular level was not clear.[9b] Another recent report details a porphyrin-derived microporous organic polymer which shows high catalytic activity for the oxidation of thiols. [10] Beyond this, there are no reports on the purposeful synthesis of metal-functionalized CMPs. Here, we report two versatile strategies for preparing metal-organic CMPs (MO-CMPs). Unlike MOFs, [2] the resulting metal-containing conjugated polymers are amorphous. Another significant difference is that the metal sites need not be nodes in the network but can also be attached pendant to the polymer chains, thus allowing the introduction of vacant metal sites and a range of chemically active functionalities. The introduction of pendant metal sites rather than metal nodes also allows the preparation of materials with unbroken extended conjugation.The MO-CMP networks were prepared either by posttreating a bipyridine-functionalized CMP precursor with a metal complex or by the direct Sonogashira-Hagihara crosscoupling of 1,3,5-triethylbenzene or 1,4-dibromobenzene and a halogenated metal-organic co-monomer. These two strategies can be defined as post-synthetic metalation and direct metal incorporation by copolymerization. The representative structures of the target MO-CMP networks are shown in Scheme 1. These polymers combine conjugation along the main chain with functional units such as bipyridine or phenylpyridine in the backbone in order to provide site...

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Metal–Organic Conjugated Microporous Polymers

et al. 2010

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“…Since then, various of TB derivatives were synthesized and applied in the eld of molecular recognition [2], chiral ligands [3][4][5], DNA probes [6,7], stereo selective catalysis [8][9][10][11][12], drug development [13,14], CO 2 capture [15,16], bioorganic chemistry [17][18][19], electroluminescent materials [20,21] and supra molecular chemistry [22] in the last two decades. Their wide range of applications is based on their huge rigidity, V-shaped twisted con guration, N-central chirality and C 2 -symmetry.…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of 1,1′-diformyl-4,4′-(6H,12H-5,11-methano-dibenzo[b,f][11,5]diazocine-2,8-diyl)dibenzene, C₂₉H₂₂N₂O₂

Qiu

Wan

Huang

et al. 2016

Zeitschrift Für Kristallographie - New Crystal Structures

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“…8 There are some reports in the literature on different applications of polymers containing Trö ger's base, which have conformationally and geometrically well-defined linker. 9,10 Because this unit has good ability to prevent the close packing of chains and decreases interchain interaction, it has been suggested that synthetic polymers, containing Trö ger's unit, can be dissolved by organic solvents. Thus, the presence of the Vshaped Trö ger's unit in the final macromolecules was thought to lead to obtain amorphous polyhydrazides, which have high solubility in organic solvents, low softening temperatures, good thermal and mechanical properties, and easy melt processability.…”

Section: Introductionmentioning

confidence: 99%

Noncoplanar rigid‐rod aromatic polyhydrazides containing Tröger's base

Abdolmaleki¹,

Heshmat-Azad²,

Kheradmand-fard³

2011

J of Applied Polymer Sci

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A new Trö ger's base-containing aromatic dihydrazide, 2,8-bis(carboxylic)-6H, 12H-5,11-methanodibenzo-[b,f] [1,5]-diazocine dihydrazide, was prepared by the condensation of ethyl p-aminobenzoate with hexamethylenetetramine in the presence of trifluoroacetic acid, followed by converting to the dihydrazide with a high yield and high purity. A series of novel aromatic polyhydrazides were prepared from the Trö ger's unit containing dihydrazide and various aromatic diacyl chlorides via low-temperature solution polycondensation in quantitative yields. All the polyhydrazides were amorphous and readily soluble at room temperature in polar organic solvents such as N,N-dimethylacetamide and N-methyl-2-pyrrolidone. These polymers could be solution cast into transparent, tough, and flexible films with good mechanical properties. They had useful levels of thermal stability associated with good glass transition temperatures (163-172 C), 10% weight-loss temperatures in excess of 460 C, and char yields at 800 C in nitrogen higher than 39%.

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Tröger’s base-functionalised organic nanoporous polymer for heterogeneous catalysis

Cited by 222 publications

References 25 publications

Metal–Organic Conjugated Microporous Polymers

Metal–Organic Conjugated Microporous Polymers

Crystal structure of 1,1′-diformyl-4,4′-(6H,12H-5,11-methano-dibenzo[b,f][11,5]diazocine-2,8-diyl)dibenzene, C₂₉H₂₂N₂O₂

Noncoplanar rigid‐rod aromatic polyhydrazides containing Tröger's base

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Tröger’s base-functionalised organic nanoporous polymer for heterogeneous catalysis

Cited by 222 publications

References 25 publications

Metal–Organic Conjugated Microporous Polymers

Metal–Organic Conjugated Microporous Polymers

Crystal structure of 1,1′-diformyl-4,4′-(6H,12H-5,11-methano-dibenzo[b,f][11,5]diazocine-2,8-diyl)dibenzene, C29H22N2O2

Noncoplanar rigid‐rod aromatic polyhydrazides containing Tröger's base

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Crystal structure of 1,1′-diformyl-4,4′-(6H,12H-5,11-methano-dibenzo[b,f][11,5]diazocine-2,8-diyl)dibenzene, C₂₉H₂₂N₂O₂