Troger's-base-derived infinite co-ordination polymer microparticles.
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ABSTRACT:
SUBMITTER: Jeon YM
PROVIDER: S-EPMC3930338 | biostudies-literature | 2009 Jan
REPOSITORIES: biostudies-literature
Publications
Tröger's-base-derived infinite co-ordination polymer microparticles.
Jeon You-Moon YM Armatas Gerasimos S GS Kim Dongwoo D Kanatzidis Mercouri G MG Mirkin Chad A CA
Small (Weinheim an der Bergstrasse, Germany) 20090101 1
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Project description:Porous organic polymers have been received considerable attention due to their heteroatom-containing structures and high surface areas, which can offer high electrochemical performance in energy applications. The majority of reported Tröger's base-functionalized porous organic polymers have been applied as effective candidates for sensing and gas separation/adsorption, while their use as electrode materials in supercapacitors is rare. Here, a novel covalent microporous organic polymer containing carbazole and Tröger's base CzT-CMOP has been successfully synthesized through the one-pot polycondensation of 9-(4-aminophenyl)-carbazole-3,6-diamine (Cz-3NH2) with dimethoxymethane. The polycondensation reaction's regioselectivity was studied using spectroscopic analyses and electronic structure calculations that confirmed the polycondensation occurred through the second and seventh positions of the carbazole unit rather than the fourth and fifth positions confirmed by first-principles calculations. Our CzT-CMOP exhibited high thermal stability of approximately 463.5 °C and a relatively high Brunauer-Emmett-Teller surface area of 615 m2 g-1 with a nonlocal density functional theory's pore size and volume of 0.48 cm3 g-1 and 1.66 nm, respectively. In addition, the synthesized CzT-CMOP displayed redox activity due to the existence of a redox-active carbazole in the polymer skeleton. CzT-CMOP revealed high electrochemical performance when used as active-electrode material in a three-electrode supercapacitor with an aqueous electrolyte of 6 M KOH, and it showed specific capacitance of 240 F g-1 at a current density of 0.5 A g-1 with excellent stability after 2000 cycles of 97% capacitance retention. Accordingly, such porous organic polymer appears to have a variety of uses in energy-related applications.
| S-EPMC8123202 | biostudies-literature
Project description:A V-Shaped 4-amino-1,8-napthalimide derived tetracarboxylic acid linker (L; bis-[N-(1,3-benzenedicarboxylic acid)]-9,18-methano-1,8-naphthalimide-[b,f][1,5]diazocine) comprising the Tröger's base (TB) structural motif was rationally designed and synthesised to access a nitrogen-rich fluorescent supramolecular coordination polymer. By adopting the straight forward precipitation method, a new luminescent nanoscale Zn(ii) coordination polymer (TB-Zn-CP) was synthesized in quantitative yield using Zn(OAc)2·2H2O and tetraacid linker L (1 : 0.5) in DMF at room temperature. The phase-purity of as-synthesised TB-Zn-CP was confirmed by X-ray powder diffraction analysis, infra-red spectroscopy, and elemental analysis. Thermogravimetric analysis suggests that TB-Zn-CP is thermally stable up to 330 °C and the morphological features of TB-Zn-CP was analysed by SEM and AFM techniques. The N2 adsorption isotherm of thermally activated TB-Zn-CP at 77 K revealed a type-II reversible adsorption isotherm and the calculated Brunauer-Emmett-Teller (BET) surface area was found to be 72 m2 g-1. Furthermore, TB-Zn-CP displayed an excellent CO2 uptake capacity of 76 mg g-1 at 273 K and good adsorption selectivity for CO2 over N2 and H2. The aqueous suspension of as-synthesized TB-Zn-CP showed strong green fluorescence (λmax = 520 nm) characteristics due to the internal-charge transfer (ICT) transition and was used as a fluorescent sensor for the discriminative sensing of nitroaromatic explosives. The aqueous suspension of TB-Zn-CP showed the largest quenching responses with high selectivity for phenolic-nitroaromatics (4-NP, 2,4-DNP and PA) even in the concurrent presence of other potentially competing nitroaromatic analytes. The fluorescence titration studies also provide evidence that TB-Zn-CP detects picric acid as low as the parts per billion (26.3 ppb) range. Furthermore, the observed fluorescence quenching responses of TB-Zn-CP towards picric acid were highly reversible. The highly selective fluorescence quenching responses including the reversible detection efficiency make the nanoscale coordination polymer TB-Zn-CP a potential material for the discriminative fluorescent sensing of nitroaromatic explosives.
| S-EPMC5452275 | biostudies-literature
Project description:Gas transport properties of PIM-EA(H?)-TB, a microporous Tröger's base polymer, were systematically studied over a range of pressure and temperature. Permeability coefficients of pure CO?, N?, CH? and H? were determined for upstream pressures up to 20 bar and temperatures up to 200 °C. PIM-EA(H?)-TB exhibited high permeability coefficients in absence of plasticization phenomena. The permeability coefficient of N?, CH? and H? increased with increasing temperature while CO2 permeability decreased with increasing temperature as expected for a glassy polymer. The diffusion and solubility coefficients were also analysed individually and compared with other polymers of intrinsic microporosity. From these results, the activation energies of permeation, diffusion and sorption enthalpies were calculated using an Arrhenius equation.
| S-EPMC6316465 | biostudies-literature
Project description: Not available
| S-EPMC8445064 | biostudies-literature
Project description:The development of efficient deep-blue emitters with thermally activated delayed fluorescence (TADF) properties is a highly significant but challenging task in the field of organic light-emitting diode (OLED) applications. Herein, we report the design and synthesis of two new 4,10-dimethyl-6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine (TB)-derived TADF emitters, TB-BP-DMAC and TB-DMAC, which feature distinct benzophenone (BP)-derived acceptors but share the same dimethylacridin (DMAC) donors. Our comparative study reveals that the amide acceptor in TB-DMAC exhibits a significantly weaker electron-withdrawing ability in comparison to that of the typical benzophenone acceptor employed in TB-BP-DMAC. This disparity not only causes a noticeable blue shift in the emission from green to deep blue but also enhances the emission efficiency and the reverse intersystem crossing (RISC) process. As a result, TB-DMAC emits efficient deep-blue delay fluorescence with a photoluminescence quantum yield (PLQY) of 50.4% and a short lifetime of 2.28 μs in doped film. The doped and non-doped OLEDs based on TB-DMAC display efficient deep-blue electroluminescence with spectral peaks at 449 and 453 nm and maximum external quantum efficiencies (EQEs) of 6.1% and 5.7%, respectively. These findings indicate that substituted amide acceptors are a viable option for the design of high-performance deep-blue TADF materials.
| S-EPMC10304498 | biostudies-literature
Project description:A detailed comparison of the gas permeability of four Polymers of Intrinsic Microporosity containing Tröger's base (TB-PIMs) is reported. In particular, we present the results of a systematic study of the differences between four related polymers, highlighting the importance of the role of methyl groups positioned at the bridgehead of ethanoanthracene (EA) and triptycene (Trip) components. The PIMs show BET surface areas between 845-1028 m2 g-1 and complete solubility in chloroform, which allowed for the casting of robust films that provided excellent permselectivities for O2/N2, CO2/N2, CO2/CH4 and H2/CH4 gas pairs so that some data surpass the 2008 Robeson upper bounds. Their interesting gas transport properties were mostly ascribed to a combination of high permeability and very strong size-selectivity of the polymers. Time lag measurements and determination of the gas diffusion coefficient of all polymers revealed that physical ageing strongly increased the size-selectivity, making them suitable for the preparation of thin film composite membranes.
| S-EPMC7231383 | biostudies-literature
Project description:Nitrogen stereocenters are common chiral units in natural products, pharmaceuticals, and chiral catalysts. However, their research has lagged largely behind, compared with carbon stereocenters and other heteroatom stereocenters. Herein, we report an efficient method for the catalytic asymmetric synthesis of Tröger's base analogues with nitrogen stereocenters via palladium catalysis and home-developed GF-Phos. It allows rapid construction of a new rigid cleft-like structure with both a C- and a N-stereogenic center in high efficiency and selectivity. A variety of applications as a chiral organocatalyst and metallic catalyst precursors were demonstrated. Furthermore, DFT calculations suggest that the NH···O hydrogen bonding and weak interaction between the substrate and ligand are crucial for the excellent enantioselectivity control.
| S-EPMC9881208 | biostudies-literature
Project description:It is highly desirable to integrate the CO2 solubility benefits of ionic liquids (ILs) in polymeric membrane systems for effective CO2 separations. Herein, we are exclusively exploring a series of four novel imidazolium-mediated Tröger's base (TB)-containing ionene polymers for enhanced CO2 separation. The two diimidazole-functionalized Tröger's base monomers synthesized from "ortho"- and "para"-substituted imidazole anilines were polymerized with equimolar amounts of two different aromatic and aliphatic comonomers (α,α'-dichloro-p-xylene and 1,10-dibromodecane, respectively) via Menshutkin reactions to obtain four respective ionene polymers ([Im-TB(o&p)-Xy][Cl] and ([Im-TB(o&p)-C10][Br], respectively). The resulting ionene polymers having halide anions were exchanged with [Tf2N]- anions, yielding a novel Tröger's base material [Im-TB(x)-R][Tf2N] or "Im-TB-Ionenes". The structural and physical properties as well as the gas separation behaviors of the copolymers of aromatic and aliphatic Im-TB-Ionenes have been extensively investigated with respect to the regiochemistry of imidazolium groups at the ortho and para positions of the TB unit. The imidazolium-mediated TB-Ionenes showed high CO2 solubility and hence an excellent CO2/CH4 permselectivity of 82.5. The Im-TB-Ionenes also displayed good thermal and mechanical stabilities.
| S-EPMC6648041 | biostudies-literature
Project description:Chiral macrocycles are an attractive subject in supramolecular chemistry because of their proven relevance in appealing applications such as asymmetric catalysis, selective absorption, or chiral recognition. Taking into account the strong topological nature of these topics, the determination of the exact 3D structure of a chiral macrocycle becomes critical to developing all of its potential usages. In this paper, we have addressed the absolute configuration determination of a Tröger's base-based triangular macrocycle, 3MC, by means of vibrational and electronic chiroptical spectroscopy with the support of DFT quantum chemistry calculations. The molecular orbital topologies, together with a dipole moment vector analysis of the electronic transitions, showed the connection between the ground and the first electronic states by means of the vibrational modes that describe the quinoidization of the side biphenyl groups. DFT ab initio methods were employed to calculate the ROA spectra of the enantiomeric pair (+)-(S,R,R)-3MC and (-)-(R,S,S)-3MC. The agreement with the recorded spectra, together with the good fitting between the experimental and theoretical Circular Intensity Difference spectra, led us to unambiguously assess the AC of this macrocycle in solution.
| S-EPMC11865959 | biostudies-literature
Project description:The rigid V-shaped Tröger's base (TB) unit has been proven efficacious in creating microporosity, making TB-based polyimides (PIs) exhibiting significant advantages in simultaneously increasing gas permeability and selectivity for the separation industry. However, TB-based PIs commonly display undesired mechanical performance due to the low molecular weight resulting from the evident steric hindrance and low reactivity of TB-containing diamines. Herein, a novel diamine-containing bisimide linkage (BIDA) has been synthesized and then polymerized with paraformaldehyde via a moderate "TB polymerization" strategy to furnish polymers simultaneously, including imide linkages and TB units in the polymer main chains, namely, TB-PIs. This TB polymerization strategy avoids the direct polymerization of dianhydride with low-reactivity TB diamine. After incorporating a meta-methyl substituent into BIDA diamine, the m-MBIDA diamine-derived m-MTBPI ultimately exhibits a high molecular weight, good tensile strength (90.4 MPa) and an outstanding fracture toughness (45.1 MJ/m3). And more importantly, the m-MTBPI membrane displays an evidently enhanced gas separation ability in comparison with BIDA-derived TBPI, with overall separation properties much closer to the 1991 Robeson upper bound. Moreover, no sign of plasticization appears for the m-MTBPI membrane when separating a high-pressure CO2/CH4 mixture (v/v = 1/1) up to 20 bar, with the CO2/CH4 mixed-gas separation performance approaching the 2018 upper bound.
| S-EPMC11859751 | biostudies-literature