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The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
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Additive Mixing of Emissive Ligands in Covalent Organic Frameworks for White Light Emission
Nyakuchena, James ; Chiromo, Humphrey ; Radpour, Shahrzad ; Guckenburg, Josh ; Huang, Jier ;
Abstract: Emissive covalent organic frameworks (COFs) are a promising class of crystalline materials that have demonstrated applications for sensing and light-emitting diodes. However, white light emission from a single COF has not been achieved yet as it requires multicomponent organic chromophores that simultaneously emit blue, green, and red light. In this work, we report the successful synthesis of a single COF with efficient white light emission by utilizing tunable emission properties of 2,1,3- benzothiadazole after incorporating different functional groups on its core structure, which results in the formation of three ligands, i.e., 4′,4-(benzothiadiazole-4,7-diyl)-dibenzaldehyde (BTD), 4,4′-(benzoselenadiazole-4,7-diyl)-dibenzaldehyde (BSD), and 4,4′-(naphtho[2,3-c][1,2,3] selenadiazole-4,9-diyl)-dibenzaldehyde (NSD), that emit in the blue, green, and red regions of the visible light spectrum. We show that white light emission can only occur when BTD, BSD, and NSD are assembled in a single COF structure due to the facilitated energy transfer process from BTD to BSD/NSD. This work demonstrates a unique approach to developing new white light-emitting materials based on the COF structure.
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Keywords: covalent ; organic ; framework ; emissive ; white ; light
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Brian P. Radka ; Taewoo Lee ; Ivan I. Smalyukh ; Timothy J. White ;
Abstract: Polymer stabilized cholesteric liquid crystals (PSCLCs) are electrically reconfigurable reflective elements. Prior studies have hypothesized and indirectly confirmed that the electro-optic response of these composites is associated with the electrically mediated distortion of the stabilizing polymer network. The proposed mechanism is based on the retention of structural chirality in the polymer stabilizing network, which upon deformation is spatially distorted, which accordingly affects the pitch of the surrounding low molar-mass liquid crystal host. Here, we utilize fluorescent confocal polarized microscopy to directly assess the electro-optic response of PSCLCs. By utilizing dual fluorescent probes, sequential imaging experiments confirm that the periodicity of the polymer stabilizing network matches that of the low molar-mass liquid crystal host. Further, we isolate distinct ion-polymer interactions that manifest in certain photopolymerization conditions.
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Purchased from AmBeed: 174350-06-2 ; 124729-02-8 ; 15155-41-6 ; 123560-48-5 ; 5720-07-0 ; 1643-19-2
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BRIAN P. RADKA ;
Abstract: Dynamic reconfiguration of optical materials has and continues to be of significant interestin technological utility in displays, healthcare, automotive, aerospace, and architecture. This thesis is concerned with so-called “polymer stabilized” cholesteric liquid crystals (PSCLCs), material systems in which application of an electric field can adjust the position or bandwidth of a selective reflection. These material systems are based upon the cholesteric liquid crystal (CLC) phase, which nascently self-organizes into a periodic helical structure in which refractive index modulation results in a polarization-specific Bragg reflection. Depending on material composition, application of an electric field to a CLC can result in reflection switching or “tuning” (e.g., shift in reflection wavelength) but typically these electro-optic responses are limited in magnitude or response time (often taking days for the reflection to recover). Comparatively, the integration of small concentrations of polymer, to “stabilize” the CLC phase, creates a material system that can undergo a dynamic and reversible electro-optic response. This thesis extends upon a number of prior examinations (generally focused on phenomena or functionality) undertaken at the Air Force Research Laboratory, that have demonstrated myriad responses including reflection bandwidth broadening, reflection wavelength tuning, and switching. The systematic investigations presented in this thesis directly elucidate the underlying electromechanical mechanism that is critical to enabling further optimization and enhancement of electro-optic response necessary for implementation in functional utility in applications. More specifically, the first aim of this thesis focuses on the formation and importance of the retention of structural chirality in the polymer stabilizing network (PSN) and the intermolecular interactions between the PSN and the non-reactive CLC host. Notably, PSCLCs prepared with non-liquid-crystalline polymer networks confirm that the chiral templating does not require the monomeric precursors to be liquid crystalline. Further, the cation-mediated electromechanical response of the deformation of the polymer network was correlated to be directly associated with the host (via distinctive confocal fluorescent experiments). The second aim of this thesis is focused on identifying and understanding the interactions between the polymer network and ions, through exploring the electrochemical properties in addition to the electro-optic response. The effect of polymerization on the electrical properties was investigated through impedance spectroscopy with mixtures prepared with metallic salts, ionic liquids, and ionic polymers. The electrical properties of these formulations were then correlated to the electro-optic response of PSCLCs prepared from them. Finally, informed by these fundamental studies, this thesis explored the molecular engineering of the polymer stabilizing network. This was achieved in two ways, both focused on affecting the crosslink density of the PSN. In the first, a dithiol additive was incorporated into the polymer network through copolymerization with the acrylate functionalized liquid crystalline monomer. This reaction decreases the crosslink density through both chain extension and chain transfer. Compositional studies isolated an optimum crosslink density/concentration to retain structural chirality with maximal elasticity. Second, a monofunctional liquid crystalline monomer was incorporated into the polymer network to decrease crosslink density while retaining high liquid crystalline character in the polymer network. The electromechanical mechanism in this material system enabled the realization of a new electro-optic phenomena in PSCLCs, reflection notch splitting
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CAS No. : | 15155-41-6 |
Formula : | C6H2Br2N2S |
M.W : | 293.97 |
SMILES Code : | BrC1=CC=C(C2=NSN=C12)Br |
MDL No. : | MFCD00658844 |
InChI Key : | FEOWHLLJXAECMU-UHFFFAOYSA-N |
Pubchem ID : | 626361 |
GHS Pictogram: |
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Signal Word: | Danger |
Hazard Statements: | H301 |
Precautionary Statements: | P264-P270-P301+P310+P330-P405-P501 |
Class: | 6.1 |
UN#: | 2811 |
Packing Group: | Ⅲ |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; toluene; at 88℃; for 13h;Reflux; Inert atmosphere; | C6H2Br2N2S (1.266 g, 4.308 mmol), C24H26BNO2, (400 mg, 1.077 mmol), Pd(PPh3)4,A mixture of K2CO3 (12.5 ml), CH3CH2OH (12.5 ml) in toluene (25.0 ml) was stirred and heated.It was refluxed at 88 C for 13 hours under a nitrogen atmosphere.The crude product was extracted three times with dichloromethane and water.It was dried over anhydrous Na 2 SO 4 .then,Using petroleum ether and dichloromethane (4:1) as the eluent,The crude product is purified by silica gel column chromatography to give the title compound.It was a pale yellow solid (yield: 62%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
38% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; at 90℃;Inert atmosphere; | 4-Octyloxyphenylboronic acid (1.02 g, 0.0041 mol), 4,7-dibromobenzo[c]-1 ,2,5-thiadiazole (compound 7, 1.20 g, 0.0041 mol), K2C03 (1.12 g, 0.0082 mol), toluene (30 ml) and water (15 ml) were all added to a 3-neck round bottomed flask and the system was evacuated, with the aid of a vacuum pump, and filled with nitrogen 3 times. Subsequently, Pd(PPh3)4 (0.24 g, 0.20 mmol) was added and the reaction mixture was heated to 90 C overnight. The reaction mixture was poured into a separating funnel, in which water (10 ml) and more toluene (10 ml) was added. The organic layer was concentrated under reduced pressure with subsequent azeotropic drying using toluene. The crude product was purified by gravity column chromatography (silica gel) using gradient elution (30% CH2CI2 in hexanes to 50% CH2CI2 in hexanes) to yield 8 as a yellow powder (0.65 g, 38%). 1 H NMR (400 MHz, CDCb): δ (ppm) 0.89 (t, 3H), 1.26-1.52 (m, 10H), 1.82 (quint, 2H), 4.04 (t, 2H), 7.05 (d, 2H), 7.53 (d, 1 H), 7.85 (d, 2H), 7.90 (d, 1 H). |
Tags: 4,7-Dibromo-2,1,3-benzothiadiazole | Other Aromatic Heterocycles | Thiadiazoles | Bromides | Polymers | Polymer Science | Drug Delivery | Organic Building Blocks | Heterocyclic Building Blocks | 15155-41-6
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