Bright polymers : Fluorescent coordination polymers made up of versatile functionalized bodipy (boron‐dipyrrin) chromophore building blocks, such as that depicted, are described. Polymerization is signaled by changes in fluorescence emission intensity and shifts in peak emission wavelengths.
Two series of new polyhedral oligomeric silsesquioxane (POSS)‐based fluorescent hybrid porous polymers, HPP‐1 and HPP‐2 , have been prepared by the Heck reaction of octavinylsilsesquioxane with 2,2′,7,7′‐tetrabromo‐9,9′‐spirobifluorene and 1,3,6,8‐tetrabromopyrene, respectively. Three sets of reaction conditions were employed to assess their effect on fluorescence. These materials exhibit tunable fluorescence from nearly no fluorescence to bright fluorescence both in the solid state and dispersed in ethanol under UV light irradiation by simply altering the reaction conditions. We speculated that the difference may be attributable to the fluorescence quenching induced by Et3N, P(o‐CH3Ph)3, and their hydrogen bromide salts employed in the reactions. This finding could give valuable suggestions for the construction of porous polymers with tunable/controllable fluorescence, especially those prepared by Heck and Sonogashira reactions in which these quenchers are used as organic bases or co‐catalysts. In addition, the porosities can also be tuned, but different trends in porosity have been found in these two series of polymers, which suggests that various factors should be carefully considered in the preparation of porous polymers with tunable/controllable porosity. Furthermore, HPP‐1 c showed moderate CO2 uptake and fluorescence that was efficiently quenched by nitroaromatic explosives, thereby indicating that these materials could be utilized as solid absorbents for the capture and storage of CO2 and as sensing agents for the detection of explosives. 相似文献
Phosphazene-containing porous materials are of a great interest due to their unique properties, caused by the synergetic presence of nitrogen and phosphorus atoms, and have found applications as adsorbents, basic catalysts, etc. On the other hand, cage-like silsesquioxanes are ideal building blocks for the preparation of covalently-linked porous materials. Here two new phosphazene-functionalized organosilsesquioxane cage-based porous polymers were synthesized successively by a Friedel-Crafts reaction of hexapyrrolylcyclotriphosphazene with octavinylsilsesquioxane in the presence of AlCl3 and CF3SO3H as catalysts. The nature of acid catalysts barely influenced the character of pores due to the interaction of catalysts with basic nitrogen atoms of phosphazene units. The obtained polymers exhibited high efficiency as metal-free catalysts for the Knoevenagel reaction. This work opens new perspectives in the use of porous polymers based on cage-like organosiloxane compounds as basic catalysts for various reactions. 相似文献
Construction of porous organic polymers (POPs) with high surface areas, well-defined nanopores, and excellent stability remains extremely challenging because of the unmanageable reaction process. Until now, only a few reported POPs have Brunauer-Emmett-Teller (BET) surface areas (SBET) exceeding 3000 m2 g−1. Herein, we demonstrate a molecular expansion strategy to integrate high surface areas, large nanopore sizes, and outstanding stability into POPs. A series of hyper-crosslinked conjugated polymers ( HCCPs ) with exceptional porosity are synthesized through this strategy. Specially, HCCP-6 and HCCP-11 exhibit the highest surface areas (SBET >3000 m2 g−1) and excellent total pore volumes (up to 3.98 cm3 g−1) among these HCCPs . They present decent total CH4 storage capacities of 491 and 421 mg g−1 at 80 bar and 298 K, respectively. Meanwhile, they are highly stable in harsh environments. The facile and general molecular expansion strategy would lead to improved synthetic routes of POPs for desired functions. 相似文献
In recent years, conjugated microporous polymers (CMPs) have become important precursors for environmental and energy applications, compared with inorganic electrode materials, due to their ease of preparation, facile charge storage process, π-conjugated structures, relatively high thermal and chemical stability, abundance in nature, and high surface areas. Therefore, in this study, we designed and prepared new benzobisthiadiazole (BBT)-linked CMPs (BBT–CMPs) using a simple Sonogashira couplings reaction by reaction of 4,8-dibromobenzo(1,2-c;4,5-c′)bis(1,2,5)thiadiazole (BBT–Br2) with ethynyl derivatives of triphenylamine (TPA-T), pyrene (Py-T), and tetraphenylethene (TPE-T), respectively, to afford TPA–BBT–CMP, Py–BBT–CMP, and TPE–BBT–CMP. The chemical structure and properties of BBT–CMPs such as surface areas, pore size, surface morphologies, and thermal stability using different measurements were discussed in detail. Among the studied BBT–CMPs, we revealed that TPE–BBT–CMP displayed high degradation temperature, up to 340 °C, with high char yield and regular, aggregated sphere based on thermogravimetric analysis (TGA) and scanning electron microscopy (SEM), respectively. Furthermore, the Py–BBT–CMP as organic electrode showed an outstanding specific capacitance of 228 F g−1 and superior capacitance stability of 93.2% (over 2000 cycles). Based on theoretical results, an important role of BBT–CMPs, due to their electronic structure, was revealed to be enhancing the charge storage. Furthermore, all three CMP polymers featured a high conjugation system, leading to improved electron conduction and small bandgaps. 相似文献
A new porous organic polymer (POP) with high thermal stability and large surface area has been synthesized and applied in the preparation of Pd/POP catalyst. Pd/POP was characterized by XRD, TGA, SEM and TEM. The catalyst consists of highly dispersed palladium nanoparticles of 0.9–4 nm size on POP with a large surface area of 650 m2/g. It presents high catalytic activity for Suzuki‐Miyaura and Sonogashira reactions. The catalyst was reusable for three to five times without significant loss of activity. 相似文献
Porous organic polymers (POPs) have been considered as prominent adsorbents for volatile iodine. So far, both crystalline and amorphous POPs have accomplished excellent iodine capture capability. Considering the difficulty and challenges in preparing perfect crystalline POPs, more explorations into developing versatile amorphous POPs are needed. Herein, amorphous POPs based on the Schiff‐base reaction were designed and synthesized for volatile iodine removal. Four amorphous POPs products named as NDB‐H , NDB‐S , ADB‐HS , and ADB‐S obtained under different solvothermal conditions were investigated in terms of their morphologies, porosity, and their iodine enrichment performance in detail. It is noteworthy that excellent efficiency for removing iodine vapor was acquired for NDB‐S (≈425 wt %), ADB‐HS (≈345 wt %), and ADB‐S (≈342 wt %). Remarkably, NDB‐H exhibited an iodine capture capacity up to ≈443 wt %. Excellent reusability was obtained as well. Amorphous NDB‐H has accomplished an extremely high iodine capture performance, illustrating the great chance to exploit versatile amorphous POPs for iodine enrichment and removal based on Schiff‐base chemistry. 相似文献
Heck coupling reactions are introduced as an efficient method to prepare porous polymers. Novel inorganic‐organic hybrid porous polymers (HPPs) were constructed via Heck coupling reactions from cubic functional polyhedral oligomeric silsesquioxanes (POSS), iodinated octaphenylsilsesquioxanes (OPS) and octavinylsilsesquioxanes (OVS) using Pd(OAc)2/PPh3 as the catalyst. Here, two iodinated OPS were used, IOPS and p‐I8OPS. IOPS was a mixture with 90% octasubstituted OPS (I8) and some nonasubstituted OPS (I9), while p‐I8OPS was a nearly pure compound with ≥99% I8 and ≥93% para‐substitution. IOPS and p‐I8OPS reacted with OVS to produce the porous materials HPP‐1 and HPP‐2, which exhibited comparable specific surface areas with SBET of 418 ± 20 m2 g−1 and 382 ± 20 m2 g−1, respectively, with total pore volumes of 0.28 ± 0.01 cm3 g−1 and 0.23 ± 0.01 cm3 g−1, respectively. HPP‐1 showed a broader pore size distribution and possessed a more significant contribution from the mesopores, when compared with HPP‐2, thereby indicating that IOPS may induce more disorder because of the geometrical asymmetry. HPP‐1 and HPP‐2 possessed moderate carbon dioxide uptakes of 134 and 124 cm3 g−1 at 1 bar at 195 K, making them promising candidates for CO2 capture and storage. The synthesized porous polymers may be easily post‐functionalized using the retained ethenylene groups.
Conjugated microporous polymers (CMPs) are a class of crosslinked polymers that combine permanent micropores with π‐conjugated skeletons and possess three‐dimensional (3D) networks. Compared with conventional materials such as metal–organic frameworks (MOFs) and covalent organic frameworks (COFs), CMPs usually have superior chemical and thermal stability. CMPs have made significant progress in heterogeneous catalysis in the past seven years. With a bottom‐up strategy, catalytic moieties can be directly introduced into in the framework to produce heterogeneous CMP catalysts. Higher activity, stability, and selectivity can be obtained with heterogeneous CMP catalysts in comparison with their homogeneous analogs. In addition, CMP catalysts can be easily isolated and recycled. In this review, we focus on CMPs as an intriguing platform for developing various highly efficient and recyclable heterogeneous catalysts in organic reactions. The design, synthesis, and structure of these CMP catalysts are also discussed in this focus review. 相似文献
In the past few decades, conjugated polymers have aroused extensive interest in organic electronic applications. The electrical performance of conjugated polymers has a close relationship with their backbone conformation. The conformation of the polymer backbone strongly affects the πelectron delocalization along polymer chains, the energy band gap, interchain interactions, and further affects charge transport properties. To realize a rigid coplanar backbone that usually possesses efficient intrachain charge transport properties and enhanced π–π stackings, such conformation control becomes a useful strategy to achieve high-performance (semi)conducting polymers. This minireview summarizes the most important polymer structures through conformation control at the molecular level, and then divides these rigid coplanar conjugated polymers into three categories: 1) noncovalent interactions locked conjugated polymers; 2) double-bond linked conjugated polymers; 3) ladder conjugated polymers. The effect of the conformation control on physical nature, optoelectronic properties, and their device performance is also discussed, as well as the challenges of chemical synthesis and structural characterization. 相似文献
Here we report a novel twisted monomer based on a distorted C?C double bond for low bandgap conjugated copolymers. This new building block provides several unique characteristics when compared to classical planar systems such as high solubility, electron accepting ability, and isomeric tunability. The resulting copolymers exhibit broad absorption spanning both visible and near‐infrared regions leading to promising solar cell performance. 相似文献
The development of porous materials is of great interest for the capture of CO2 from various emission sources, which is essential to mitigate its detrimental environmental impact. In this direction, porous organic polymers (POPs) have emerged as prime candidates owing to their structural tunability, physiochemical stability and high surface areas. In an effort to transfer an intrinsic property of a cyclotetrabenzoin-derived macrocycle – its high CO2 affinity – into porous networks, herein we report the synthesis of three-dimensional (3D) macrocycle-based POPs through the polycondensation of an octaketone macrocycle with phenazine-2,3,7,8-tetraamine hydrochloride. This polycondensation was performed under ionothermal conditions, using a eutectic salt mixture in the temperature range of 200 to 300 °C. The resulting polymers, named 3D-mmPOPs, showed reaction temperature-dependent surface areas and gas uptake properties. 3D-mmPOP-250 synthesized at 250 °C exhibited a surface area of 752 m2 g−1 and high microporosity originating from the macrocyclic units, thus resulting in an excellent CO2 binding enthalpy of 40.6 kJ mol−1 and CO2 uptake capacity of 3.51 mmol g−1 at 273 K, 1.1 bar. 相似文献