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PROBING CHARGE TRANSPORT MECHANISMS IN 2D SEMICONDUCTIVE METAL ORGANIC FRAMEWOKS
James Nyakuchena ;
Abstract: Metal organic frameworks (MOFs) are a class of highly porous crystalline materials constructed from metal nodes connected by multitopic organic ligands. Due to their unique properties such as large surface area, tunable pore structure, and structural diversity, they have demonstrated potential in a wide array of applications including gas storage and separation, sensing, catalysis, and drug delivery. However, there are only a handful of MOFs reported that have electrical conductivity, which prevents their applications in photoelectronic and photocatalytic applications. This is because hard metals and redox inactive ligands with terminal hard linking bases such as carboxylates are often used in constructing these materials. In addition, the porous nature of these materials leaves voids between the polymeric chains, which cuts off communication between the densely packed units. It was not until recently that MOFs with charge conductivity were reported after replacing the hard-linking nodes with soft acid/base counterparts. However, the charge transport mechanism that is responsible for their conductivity remains poorly understood. The objective of my research projects is to have a fundamental understanding of charge transport mechanisms in MOFs to facilitate their applications in photo-electronics and photocatalysis. In this report, I will discuss fundamental insights into charge transport mechanisms in 2D M-THQ MOFs (M= Cu, Fe, Ni, and Zn) (chapters 3 and 4) and 1D pyrene-tetra thiol-based nanosheets (chapter 6). Chapter 3 focuses on the experimental evidence of through bond charge transport in Cu-THQ semiconductive MOF through a combination of spectroscopic techniques and DFT calculation. Chapter 4 reports the dependence of exciton dynamics and band structure engineering on metal nodes in M-THQ MOF (M= Fe, Ni, and Zn). Chapter 5 discusses the impact of Ligand size in 2D MOFs on photoconduction and charge transport mechanisms. In Chapter 6 I discuss the design and synthesis of 1D pyrene-tetra thiol-based MOFs, and the impact of pi-pi stacking on photoconduction. I also synthesized a new sulfur-decorated MOF for potential application in metal ion batteries and white light emissive COFs which will be discussed in chapters 7 and 8. Finally, chapter 9 outlines the future directions of this project.
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CAS No. : | 122775-35-3 |
Formula : | C8H11BO4 |
M.W : | 181.98 |
SMILES Code : | OB(C1=CC=C(OC)C(OC)=C1)O |
MDL No. : | MFCD01074574 |
InChI Key : | RCVDPBFUMYUKPB-UHFFFAOYSA-N |
Pubchem ID : | 2734702 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
* 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 |
---|---|---|
With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; N,N-dimethyl-formamide; at 100℃;Inert atmosphere; Sealed tube; | Preparative Example 24PREPARATION OF 5-(3,4-DIMETHOXYPHENYL)THIOPHENE-2-SULFONAMIDEA stirred solution of 5-bromothiophene-2-sulfonamide (2 g, 8.26 mmol) and (3,4-dimethoxyphenyl)boronic acid (1.8 g, 9.90 mmol) in 30 mL DMF at room temperature was purged with N2 gas for 10 mins. To this stirred solution was added (Ph3P)4Pd (1.9 g, 1.65 mmol) and saturated Na2CO3/H2O (2.63 g, 3 mmol). The N2 purge was stopped and the reaction mixture was sealed and heated with a preheated oil bath at 100 C. overnight. The reaction mixture was filtered and the filtrate was partitioned between saturated NaHCO3 and EtOAc, the layers were separated, and the aqueous layer was extracted again with EtOAc. The combined organic layers were dried (MgSO4), filtered, and evaporated in vacuo. The resulting material was purified by silica gel chromatography (40% EtOAc in hexane) to provide the product, as a light yellow solid.1H NMR (500 MHz, CD3OD) δ (ppm): 7.56 (d, 1H), 7.30 (d, 1H), 7.24 (m, 2H), 7.00 (d, 1H), 3.90 (d, 6H). | |
With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; N,N-dimethyl-formamide; at 20 - 100℃;Sealed tube; | PREPARATIVE EXAMPLE 10 PREPARATION OF 5-(3,4-DIMETHOXYPHENYL)THTOPHENE-2-SULFON AMIDEA stirred solution of 5-bromothiophene-2-suIfonamide (2 g, 8.26 mmol) and (3,4- dimethoxyphenyl)boronic acid (1.8 g, 9.90 mmol) in 30 mL DMF at room temperature was purged with N2 gas for 10 mins. To this stirred solution was added (Ph3P)4Pd (1.9 g, 1.65 mmol) and saturated Na2CO3/H2θ (2.63 g, 3 mmol). The N2 purge was stopped and the reaction mixture was sealed and heated with a preheated oil bath at 1000C overnight. The reaction mixture was filtered and the filtrate was partitioned between saturated NaHCO3 and EtOAc, the layers were separated, and the aqueous layer was extracted again with EtOAc. The combined organic layers were dried (MgSO^), filtered, and evaporated in vacuo. The resulting material was purified by silica gel chromatography (40% EtOAc in hexane) to provide the product, as a light yellow solid.1H NMR (500 MHz, CD3OD) δ (ppm): 7.56 (d, IH), 7.30 (d, IH), 7.24 (m, 2H), 7.00 (d, IH), 3.90 (d,SH). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium hydroxide;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; at 20 - 85℃; for 24.0833h; | To a solution of 4-BROMOPHENETHYLAMINE (10G, 48. 98mmol) in anhydrous DMF (150mL), containing anhydrous triethylamine (35mL, 244.9 mol), was added BOC2O. The reaction mixture was heated for 15 minutes at 50C. After cooling to room temperature, brine (100ML) and HCI (1N, 100ML) were added subsequently, and the mixture was extracted several times with ether. The recombined organic layer was washed again with brine, dried over sodium sulfate, filtered and evaporated. The crude was flashed with 10% ethyl acetate in hexanes to give the [2- (4-BROMO-PHENYL)-ETHYL]-CARBAMIC acid tert-butyl ester.'H NMR (CDCI3, 300MHZ) : 1.41 (s, 9H); 2.22 (t, J=7. 1HZ, 2H); 3.31 (m, 2H); 4.67 (s, broad, 1 H); 7.03 (d, J=8.2Hz, 2H); 7.38 (d, J=8.2Hz, 2H). A mixture of the above mentioned compound (1. 00g, 3. 33MMOL), 3, 4-DIMETHOXYPHENYLBORONIC acid (1. 21 G, 6. 66MMOL), and potassium hydroxide (2N, 5mL, 10MMOL) in THF (15mL) was degassed using argon for 5 minutes. Palladium tetrakis-triphenylphosphine (200mg, 0. 167MMOL) was added and the mixture was heated at 85C. After 24 hours, the reaction mixture was allowed to cool to room temperature. Brine (20mL) was added and the reaction mixture was extracted several times with ether. The recombined organic phase was extracted with brine, dried over sodium sulfate, filtered, and evaporated. Silica gel chromatography of the crude using 20% ethyl acetate/n-hexane afforded [2- (3', 4'-DIMETHOXY-BIPHENYL-4YL)-ETHYLAMINE]-CARBAMIC acid tert-butyl ester as a white SOLID. 1H-NMR (CDCI3, 300MHZ) : 1.44 (s, 9H); 2.82 (t, J=6.9Hz, 2H); 3.39 (m, 2H); 3.91 (s, 3H); 3.93 (s, 3H); 4.67 (s, broad, 1H) ; 6.92 (d, J=8.2Hz, 1 H) ; 7.11 (m, 2H); 7.25 (m, 2H); 7.48 (d, J=8. 1 Hz, 2H). A solution of the above mentioned compound (1.14g, 3. 19mmol) in anhydrous methanol (50mL) was cooled in ice bath and then treated drop wise with acetyl chloride. Stirring was continued for 30 minutes at the same temperature followed by overnight stirring at room temperature. About 30mL of the solvent was removed by evaporation and the mixture was diluted with 200mL of ether. The entitled product was collected as a white solid by filtration, followed by washing with anhydrous ether and drying under high VACUUM.'H-NMR (D20, 300MHZ) : 2.80 (t, J=6.9Hz, 2H); 3.40 (m, 2H); 3.91 (s, 3H); 3.93 (s, 3H); 4.77 (s, broad, 1H) ; 7.00 (d, J=8.2Hz, 1H) ; 7.15 (m, 2H); 7.26 (m, 2H); 7.50 (d, J=8. 1HZ, 2H) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; for 3h;Heating / reflux;Product distribution / selectivity; | Method A: To a solution of 6-chloro-pyrido[3,2-d]pyrimidin-4(3H)-one (200 mg,1.1 mmol) in 1 ,4-dioxane (20 ml) and water (10 ml) was added 3,4-dimethoxyphenyl boronic acid (240 mg, 1.32 mmol), potassium carbonate (380 mg, 2.75 mmol) and tetrakis(triphenylphosphine)palladium(0) (63 mg, 0.055 mmol). The reaction mixture was refluxed for 3 hours, cooled down to room temperature and the solvents were evaporated in vacuo. The residue was adsorbed on silica, purified by silica gel column chromatography (the mobile phase being a acetone/dichloromethane mixture, in a ratio gradually ranging from 30:70 to 40:60) and characterised by its mass spectrum as follows : MS (m/z) : 284 ([M+H]+, 100).Method B: A suspension of 2-carboxamido-3-amino-6-(3,4-dimethoxyphenyl)- pyridine (770 mg, 2.8 mmol) in triethyl orthoformate (28 ml) was refluxed for 12 hours. Then, the reaction mixture was cooled down and evaporated to dryness. The residue was purified by silica gel column chromatography (the mobile phase being an ethyl acetate/hexane mixture in a ratio gradually ranging from 2:8 to 3:7), resulting in the pure title compound (530 mg, yield 67 %) which was characterised by its mass spectrum as follows: MS (m/z) : 284 ([M+H)+, 100]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 80℃; for 16h; | Example 3: Preparation of [6-(3,4-Dimethoxy-phenyI)-quinazolin-4-yI]-(4- morpholin-4-yl-phenyI)-ammeStep 1: 4-Amino-3',4'-dimethoxy-biphenyl-3-carbonitrileA mixture of 3,4-dimethoxyboronic acid (956mg, 2eq), intermediate 1 ( 640mg, leq), tetrakis (triphenylphosphine) palladium (0) (10%, 303mg) in DME / 2M aq sodium carbonate ( 2:1, 21ml) was heated to 80 for 16h.The cooled reaction mixture was diluted with ethyl acetate and washed with further aq sodium carbonate then water. The dried organic phase was concentrated to a dark red gum which was dissolved in CH2Cl2 and loaded onto a SPE cartridge ( Si5 2Og) and eluted with CH2Cl2. The major fractions containing product were combined and concentrated to a semi-solid which was triturated with diethyl ether and the desired compound isolated by filtration as a light brown solid (296mg5 44%) EPO <DP n="20"/>LC-MS rt 2.73 no ion observed1H (DMSO) 57.77 (IH, s), 7.71 (IH, d), 7.2 (IH5 s), 7.17 (IH5 d), 7.03 (IH, d), 6.91(IH5 d). 6.17 (2H5 br s), 3.89 (3H5 s), 3.83 (3H5 s) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46% | With N,N-dimethyl-formamide; In acetonitrile; at 100℃; for 0.333333h;Microwave irradiation; | A mixture of <strong>[518057-72-2]3-amino-6-fluorobenzamide</strong> (85 mg, 0.5 mmol), 3,4-dimethoxyphenylboronic acid (91 mg, 0.5 mmol) and glyoxylic acid monohydrate (46 mg, 0.5 mmol) in acetonitrile (2.0 mL) and DMF (0.2 mL) was heated at 100 C. for 20 min. in a microwave reactor. After removal of solvent, the crude was triturated with methylene chloride. The precipitate formed was collected by filtration and washed with methylene chloride to give 13A after drying, yield: 46%. 1H NMR (400 MHz, Methanol-d4) delta ppm 3.81 (s, 3H) 3.82 (s, 3H) 4.92 (s, 1H) 6.83-6.89 (m, 1H) 6.93 (d, J=8.35 Hz, 1H) 6.96-7.02 (m, 1H) 7.03-7.07 (m, 1H) 7.10 (d, J=1.76 Hz, 1H) 7.15 (dd, J=5.93, 2.86 Hz, 1H), LCMS: 349 (M+1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In methanol; water; toluene;Inert atmosphere; Reflux; | General procedure: To a solution of bromobiphenylaldehyde (6, 260 mg, 1 mmol) and various phenyl boronic acids (7a-j, 1 mmol) in 2 M aqueous sodium carbonate (2 mL) and toluene/ethanol (9:3 mL) is added a catalytic amount (0.4% mol) of tetrakis-triphenylphosphine palladium, and the mixture was reflux under argon atmosphere for 2-3 h. After completion of reaction, the suspension is cooled and extracted with ethyl acetate (3 × 30 mL) and the organic phase was washed with water and brine, dried over anhydrous Na2SO4 and the solvent was removed under reduced pressure to get the crude product. This residue was further purified by column chromatography using ethyl acetate and hexane to afford the pure terphenylaldehydes (8). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
20% | In ethyl acetate; | Example 5 Synthesis of SA-59, SA-60 and SA-61 3-bromo-2,5-bis(3',4'-dimethoxyphenyl)thiophene (18) was prepared by the reaction of <strong>[3141-24-0]2,3,5-tribromothiophene</strong> (17) (321 mg, 1 mmol) and (3,4-dimethoxyphenyl)boronic acid (15) (419 mg, 2.3 mmol) according to the similar procedure for compound 16. The reaction mixture was purified by column chromatography (10%-30% EtOAc in hexanes) and afforded 18 (337 mg, 77% yield) as a yellow solid. SA-60 was also isolated (97 mg, 20% yield) from the reaction above as a dark yellow solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | In ethyl acetate; | Example 6 Synthesis of SA-62 Compound 19 was prepared by the reaction of 2,5-dibromothiophene (17) (1.14 g, 5.24 mmol) and (3,4-dimethoxyphenyl)boronic acid (15) (910 mg, 5 mmol) according to the similar procedure for compound 16. The reaction mixture was purified by flash column chromatography (FCC) (5%-20% EtOAc in hexanes) and afforded compound 19 (509 mg, 34% yield) as a yellowish crystal. Compound 16 was also isolated (578 mg, 65% yield) as a yellow solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 1,1'-bis-(diphenylphosphino)ferrocene; tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In 1,4-dioxane; toluene; for 12h;Reflux; | General procedure: A mixture of 2-chloro-4-(trifluoromethyl)-benzonitrile (1.00 mmol), appropriate boronic acid (1.20 mmol)were dissolved in toluene/dioxane:2 N Na2CO3 (2:1:1) solution(6 ml). Tetrakis(triphenyl-phosphine)palladium(0) (0.10 mmol)and 1,10-Ferrocenediyl-bis(diphenylphosphine) (0.20 mmol) wasadded to the mixture and it was refluxed for 12 h. After cooleddown to ambient temperature, the reaction was filtered over celiteand extracted with EtOAc twice. The combined organic extractswere dried over MgSO4, filtered, and concentrated in vacuo. Theresidue was purified by flash column chromatography on silicagel using EtOAc/hexanes (1:10) eluant condition. (R-B(OH)2 =1-pentenyl boronic acid for 53, 1-cyclohexenylboronicacid for 54). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; at 75℃;Inert atmosphere; | General procedure: In 25 mL round bottom flask equipped with reflux condenser, 0.0004 mol of 4-chloro-3,5-dimethylphenol mixed with appropriate quantity of arylboronic acid (1-6) and 0.05 g of Pd(PPh3)4 were added into the flask containing 20 mL of absolute ethanol under inert atmospheric condition (N2) gas. The mixture was stirred and heated and 5 mL of solution (5% Na2CO3) were added into the flask.The reaction mixture was stirred and heated at 75 C for 5-6 h then followed by TLC and monitor reactions using (n-hexane and ethyl acetate) in 2:3 ratio v/v. The mixture was filtrated off to remove the inorganic salt and the residue of pallidum catalyst, washed by cooled ethanol and the solvent was removed and decanted by cooled ether (Scheme-I). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With [2,2]bipyridinyl; potassium fluoride; palladium diacetate; trifluoroacetic acid; In tetrahydrofuran; water; at 80℃; for 2h;Inert atmosphere; Schlenk technique; | General procedure: Under a nitrogen atmosphere, aryl acetonitrile 1 (3mmol), arylboronic acids 2 (6mmol), palladium acetate (5mol %), 2,2′-Bipyridine (10mol %), trifluoroacetic acid (30mmol), potassium fluoride (6mmol), tetrahydrofuran (20mL), and water (10mL) were successively added to a Schlenk reaction tube. The reaction mixture was stirred vigorously at 80C for 2h. After the reaction mixture was cooled to room temperature, saturated sodium bicarbonate (30mL) was added into the solution, and the mixture was extracted with ethyl acetate (10mL) for 3 times. The combined organic layer was concentrated in vacuo. The residue was purified by flash column chromatography to afford desired product 3. |