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Structure of 3109-63-5

Chemical Structure| 3109-63-5

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Deng, Chun-Lin ; Tra, Bi Youan E ; Zhang, Xibao ; Zhang, Chonghe ; Gilliard Jr, Robert J ;

Abstract: Achieving efficient red and near-infrared (NIR) emission in boron cation-based emitters remains challenging owing to their intrinsic instability, strong electrophilicity of the boron centre and pronounced non-radiative decay governed by the energy gap law. Here we report a family of air- and moisture-stable carbodicarbene (CDC)-borabenzo[c]anthanthrenium ions exhibiting solid-state red-to-NIR luminescence (maximum emission wavelength up to 730 nm) with competitive quantum yields. Crystallographic, photophysical and computational analyses reveal that the CDC ligand plays a dual role by electronically stabilizing the boron centre and directing ion-pair assembly via charge localization, thereby modulating exciton coupling and aggregate-state emission. These cationic π-extended boron frameworks represent rare examples of monoboron-doped luminophores displaying deep-red-to-NIR emission. Our findings highlight that the combination of π-extension, a charge-directing CDC ligand and ion-pair assembly constitutes an effective strategy to access efficient red/NIR emitters, providing guiding principles for the design of functional long-wavelength emitting main-group materials.

Purchased from AmBeed: ; ;

Orr, Andre D ; Zhu, Zhengbo ; Durand, Nicolas ; Bonfiglio, Anna ; Teitsworth, Taylor S ; Sampaio, Renato N , et al.

Abstract: We present the first examples of installing a redox reporter and CO2 reduction (CO2R) catalyst onto freshly HF-etched Si (photo)electrodes using a solution-phase nitrocyclocondensation (NCC) reaction. Previous studies detailed the mechanism of NCC reactions on Si under ultrahigh vacuum conditions but have not applied these chemistries to generate functional (photo)electrodes. Installing 4-nitrophenyl ferrocene (4-NpFc) molecules directly onto degenerately doped p+Si allowed us to evaluate the effects of different NCC reaction conditions on coverage (e.g., 3.6 ± 1.2 × 10−11 mol/cm2) and electrochemical reversibility. The 4-NpFc molecules remained immobilized under the reducing potentials (−2.0 V vs Fc+/0 in acetonitrile) needed to drive molecular CO2R catalysts. Installing 4-nitroaniline (4-NA) molecules onto low-doped pSi allowed us to couple Lehn-type Re(I) catalysts with pendant carboxylic acids. The CO Faradaic efficiency of CO production under 1-sun illumination (−2.15 V vs Fc+/0) was 23% in CO2-saturated electrolyte, a value that surpasses previous examples of CO2R catalyst monolayers on Si. These two examples highlight the versatility of solution-phase NCC attachment chemistries for generating functional Si (photo)electrodes.

Keywords: photoelectrode ; cathode ; silicon ; semiconductor ; solar fuel ; catalysis ; surface chemistry

Purchased from AmBeed:

Teitsworth, Taylor S ; Fang, Hui ; Harvey, Alexis K ; Orr, Andre D ; Donley, Carrie L ; Fakhraai, Zahra , et al.

Abstract: Aryl diazonium electrografting is a powerful method for imparting molecular functionality onto various substrates by forming a stable carbon-surface covalent bond. While the high reactivity of the aryl radical intermediate makes this method fast and reliable, it can also lead to the formation of an insulating and disordered multilayer film. These thick films affect electrochemical performance, especially for semiconductor substrates used in photoelectrochemical applications. We studied the effects of film thickness and composition by electrografting in situ-generated aminobenzene diazonium salts onto both n-type and p-type silicon electrodes at fixed potentials. Next, we attached to the amine-terminated films and probed their (photo)electrochemical behavior. Cyclic voltammetry measurements showed decreased electrochemical reversibility with increasing diazonium film thickness; this reversibility was restored when was incorporated throughout the film with a layer-by-layer deposition process. Finally, we compared the behavior of dark p-type electrodes to n-type photoelectrodes and observed differences in the electrochemical reversibility that we attribute to the change in potential drop across the two interfaces.

Purchased from AmBeed:

Qing Yun Li ; Leigh Anna Hunt ; Kalpani Hirunika Wijesinghe ; Christine Curiac ; Ashley Williams ; Amala Dass , et al.

Abstract: Strong photoinduced oxidants are important to organic synthesis and solar energy conversion, to chemical fuels or electric. For these applications, visible light absorption is important to solar energy conversion and long-lived excited states are needed to drive catalysis. With respect to these desirable qualities, a series of five 5,6-dicyano[2,1,3]benzothiadiazole (DCBT) dyes are examined as organic chromophores that can serve as strong photooxidants in catalytic systems. The series utilizes a DCBT core with aryl groups on the periphery with varying electron donation strengths relative to the core. The dyes are studied via both steady-state and transient absorption and emission studies. Additionally, computational analysis, voltammetry, crystallography, and absorption spectroelectrochemistry are also used to better understand the behavior of these dyes. Ultimately, a strong photooxidant is arrived at with an exceptionally long excited state lifetime for an organic chromophore of 16 µs. The long-lived excited state photosensitizer is well-suited for use in catalysis, and visible light driven photosensitized water oxidation is demonstrated using a water-soluble photosensitizer.

Purchased from AmBeed: ; ; ; ; ; ; ; ; ; ; ; 51364-51-3 ; 538-75-0 ; 584-08-7 ; 1122-91-4 ; 123-30-8 ; 108-88-3 ; 109-77-3 ; 64-19-7 ; 603-35-0

Matthew T. Fortunato ; Curtis E. Moore ; Claudia Turro ;

Abstract: A new series of Rh2(II,II) complexes with the formula cis-[Rh2(DTolF)2(bpnp)(L)]2+, where bpnp = 2,7-bis(2-pyridyl)-1,8-naphthyridine, DTolF = N,N′-di(p-tolyl) formamidinate, and L = pdz (pyridazine; 2), cinn (cinnoline; 3), and bncn (benzo[c]cinnoline; 4), were synthesized from the precursor cis-[Rh2(DTolF)2(bpnp)(CH3CN)2]2+ (1). The first reduction couple in 2–4 is localized on the bpnp ligand at approximately −0.52 V vs Ag/AgCl in CH3CN (0.1 M TBAPF6), followed by reduction of the corresponding diazine ligand. Complex 1 exhibits a Rh2(δ*)/DTolF → bpnp(π*) metal/ligand-to-ligand charge-transfer (1ML-LCT) absorption with a maximum at 767 nm (ε = 1800 M–1 cm–1). This transition is also present in the spectra of 2–4, overlaid with the Rh2(δ*)/DTolF → L(π*) 1ML-LCT bands at 516 nm in 2 (L = pdz), 640 nm in 3 (L = cinn), and 721 nm in 4 (L = bncn). Complexes 2 and 3 exhibit Rh2(δ*)/DTolF → bpnp 3ML-LCT excited states with lifetimes, τ, of 3 and 5 ns, respectively, in CH3CN, whereas the lowest energy 3ML-LCT state in 4 is Rh2(δ*)/DTolF → bncn in nature with τ = 1 ns. Irradiation of 4 with 670 nm light in DMF in the presence of 0.1 M TsOH (p-toluene sulfonic acid) and 30 mM BNAH (1-benzyl-1,4-dihydronicotinamide) results in the production of H2 with a turnover number (TON) of 16 over 24 h. The axial capping of the Rh2(II,II) bimetallic core with the bpnp ligand prevents the formation of an Rh–H hydride intermediate. These results show that the observed photocatalytic reactivity is localized on the bncn ligand, representing the first example of ligand-centered H2 production.

Purchased from AmBeed: ; ; ; ;

Prince K. Verma ; Connor A. Koellner ; Hailey Hall ; Meagan R. Phister ; Kevin H. Stone ; Asa W. Nichols , et al.

Abstract: Solution shearing, a meniscus-guided coating process, can create large-area metal–organic framework (MOF) thin films rapidly, which can lead to the formation of uniform membranes for separations or thin films for sensing and catalysis applications. Although previous work has shown that solution shearing can render MOF thin films, examples have been limited to a few prototypical systems, such as HKUST-1, Cu-HHTP, and UiO-66. Here, we expand on the applicability of solution shearing by making thin films of NU-901, a zirconium-based MOF. We study how the NU-901 thin film properties (i.e., crystallinity, surface coverage, and thickness) can be controlled as a function of substrate temperature and linker concentration. High fractional surface coverage of small-area (∼1 cm2) NU-901 thin films (0.88 ± 0.06) is achieved on a glass substrate for all conditions after one blade pass, while a low to moderate fractional surface coverage (0.73 ± 0.18) is obtained for large-area (∼5 cm2) NU-901 thin films. The crystallinity of NU-901 crystals increases with temperature and decreases with linker concentration. On the other hand, the adjusted thickness of NU-901 thin films increases with both increasing temperature and linker concentration. We also extend the solution shearing technique to synthesize MOF-525 thin films on a transparent conductive oxide that are useful for electrocatalysis. We show that Fe-metalated MOF-525 films can reduce CO2 to CO, which has implications for CO2 capture and utilization. The demonstration of thin film formation of NU-901 and MOF-525 using solution shearing on a wide range of substrates will be highly useful for implementing these MOFs in sensing and catalytic applications.

Keywords: metal−organic framework ; thin films ; solution shearing ; NU-901 ; MOF-525 ; electrocatalysis

Purchased from AmBeed:

Han, Guanqun ;

Abstract: Mankind's sustainable development not only requires the capture and conversion of renewable energies but also necessitates the production of chemical goods from renewable carbon sources. Biomass is the only accessible and renewable carbon source. One major class of biomass is degradative small molecules, among which 5-hydroxymethylfurfural (HMF) is considered as a platform chemical and it can serve as a starting material to produce various upgrading compounds, eg, the oxidation products, 2, 5-furan dicarboxylic acid (FDCA), and 2, 5-diformylfuran (DFF), can act as biopolymer precursors. In this dissertation, we successfully demonstrated that ultrathin Ni/CdS nanosheets can be efficient photocatalyst to produce value-added bioproducts (eg, furoic acid, DFF, and FDCA) from biomass-derived molecules. Even more desirable is that the oxidative biomass upgrading can be integrated with H2 production.

Purchased from AmBeed: ; ; ; ; ; ;

Alternative Products

Product Details of [ 3109-63-5 ]

CAS No. :3109-63-5
Formula : C16H36F6NP
M.W : 387.43
SMILES Code : CCCC[N+](CCCC)(CCCC)CCCC.F[P-](F)(F)(F)(F)F
MDL No. :MFCD00011748
InChI Key :BKBKEFQIOUYLBC-UHFFFAOYSA-N
Pubchem ID :165075

Safety of [ 3109-63-5 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Computational Chemistry of [ 3109-63-5 ] Show Less

Physicochemical Properties

Num. heavy atoms 24
Num. arom. heavy atoms 0
Fraction Csp3 1.0
Num. rotatable bonds 12
Num. H-bond acceptors 6.0
Num. H-bond donors 0.0
Molar Refractivity 94.97
TPSA ?

Topological Polar Surface Area: Calculated from
Ertl P. et al. 2000 J. Med. Chem.

13.59 Ų

Lipophilicity

Log Po/w (iLOGP)?

iLOGP: in-house physics-based method implemented from
Daina A et al. 2014 J. Chem. Inf. Model.

0.0
Log Po/w (XLOGP3)?

XLOGP3: Atomistic and knowledge-based method calculated by
XLOGP program, version 3.2.2, courtesy of CCBG, Shanghai Institute of Organic Chemistry

3.87
Log Po/w (WLOGP)?

WLOGP: Atomistic method implemented from
Wildman SA and Crippen GM. 1999 J. Chem. Inf. Model.

10.91
Log Po/w (MLOGP)?

MLOGP: Topological method implemented from
Moriguchi I. et al. 1992 Chem. Pharm. Bull.
Moriguchi I. et al. 1994 Chem. Pharm. Bull.
Lipinski PA. et al. 2001 Adv. Drug. Deliv. Rev.

1.48
Log Po/w (SILICOS-IT)?

SILICOS-IT: Hybrid fragmental/topological method calculated by
FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com

4.71
Consensus Log Po/w?

Consensus Log Po/w: Average of all five predictions

4.19

Water Solubility

Log S (ESOL):?

ESOL: Topological method implemented from
Delaney JS. 2004 J. Chem. Inf. Model.

-3.89
Solubility 0.0501 mg/ml ; 0.000129 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Soluble
Log S (Ali)?

Ali: Topological method implemented from
Ali J. et al. 2012 J. Chem. Inf. Model.

-3.85
Solubility 0.0544 mg/ml ; 0.00014 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Soluble
Log S (SILICOS-IT)?

SILICOS-IT: Fragmental method calculated by
FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com

-6.35
Solubility 0.000174 mg/ml ; 0.000000449 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Poorly soluble

Pharmacokinetics

GI absorption?

Gatrointestinal absorption: according to the white of the BOILED-Egg

Low
BBB permeant?

BBB permeation: according to the yolk of the BOILED-Egg

No
P-gp substrate?

P-glycoprotein substrate: SVM model built on 1033 molecules (training set)
and tested on 415 molecules (test set)
10-fold CV: ACC=0.72 / AUC=0.77
External: ACC=0.88 / AUC=0.94

Yes
CYP1A2 inhibitor?

Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set)
and tested on 3000 molecules (test set)
10-fold CV: ACC=0.83 / AUC=0.90
External: ACC=0.84 / AUC=0.91

No
CYP2C19 inhibitor?

Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set)
and tested on 3000 molecules (test set)
10-fold CV: ACC=0.80 / AUC=0.86
External: ACC=0.80 / AUC=0.87

No
CYP2C9 inhibitor?

Cytochrome P450 2C9 inhibitor: SVM model built on 5940 molecules (training set)
and tested on 2075 molecules (test set)
10-fold CV: ACC=0.78 / AUC=0.85
External: ACC=0.71 / AUC=0.81

No
CYP2D6 inhibitor?

Cytochrome P450 2D6 inhibitor: SVM model built on 3664 molecules (training set)
and tested on 1068 molecules (test set)
10-fold CV: ACC=0.79 / AUC=0.85
External: ACC=0.81 / AUC=0.87

No
CYP3A4 inhibitor?

Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set)
and tested on 2579 molecules (test set)
10-fold CV: ACC=0.77 / AUC=0.85
External: ACC=0.78 / AUC=0.86

No
Log Kp (skin permeation)?

Skin permeation: QSPR model implemented from
Potts RO and Guy RH. 1992 Pharm. Res.

-5.92 cm/s

Druglikeness

Lipinski?

Lipinski (Pfizer) filter: implemented from
Lipinski CA. et al. 2001 Adv. Drug Deliv. Rev.
MW ≤ 500
MLOGP ≤ 4.15
N or O ≤ 10
NH or OH ≤ 5

0.0
Ghose?

Ghose filter: implemented from
Ghose AK. et al. 1999 J. Comb. Chem.
160 ≤ MW ≤ 480
-0.4 ≤ WLOGP ≤ 5.6
40 ≤ MR ≤ 130
20 ≤ atoms ≤ 70

None
Veber?

Veber (GSK) filter: implemented from
Veber DF. et al. 2002 J. Med. Chem.
Rotatable bonds ≤ 10
TPSA ≤ 140

1.0
Egan?

Egan (Pharmacia) filter: implemented from
Egan WJ. et al. 2000 J. Med. Chem.
WLOGP ≤ 5.88
TPSA ≤ 131.6

1.0
Muegge?

Muegge (Bayer) filter: implemented from
Muegge I. et al. 2001 J. Med. Chem.
200 ≤ MW ≤ 600
-2 ≤ XLOGP ≤ 5
TPSA ≤ 150
Num. rings ≤ 7
Num. carbon > 4
Num. heteroatoms > 1
Num. rotatable bonds ≤ 15
H-bond acc. ≤ 10
H-bond don. ≤ 5

0.0
Bioavailability Score?

Abbott Bioavailability Score: Probability of F > 10% in rat
implemented from
Martin YC. 2005 J. Med. Chem.

0.55

Medicinal Chemistry

PAINS?

Pan Assay Interference Structures: implemented from
Baell JB. & Holloway GA. 2010 J. Med. Chem.

0.0 alert
Brenk?

Structural Alert: implemented from
Brenk R. et al. 2008 ChemMedChem

2.0 alert: heavy_metal
Leadlikeness?

Leadlikeness: implemented from
Teague SJ. 1999 Angew. Chem. Int. Ed.
250 ≤ MW ≤ 350
XLOGP ≤ 3.5
Num. rotatable bonds ≤ 7

No; 1 violation:MW<3.0
Synthetic accessibility?

Synthetic accessibility score: from 1 (very easy) to 10 (very difficult)
based on 1024 fragmental contributions (FP2) modulated by size and complexity penaties,
trained on 12'782'590 molecules and tested on 40 external molecules (r2 = 0.94)

2.49

Application In Synthesis of [ 3109-63-5 ]

* 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.

  • Downstream synthetic route of [ 3109-63-5 ]

[ 3109-63-5 ] Synthesis Path-Downstream   1~4

  • 1
  • [ 87761-77-1 ]
  • [ 3109-63-5 ]
  • [ 607-01-2 ]
  • [ 93427-02-2 ]
  • 2
  • [ 1689-83-4 ]
  • [ 3109-63-5 ]
  • [ 902093-08-7 ]
  • [ 2296-23-3 ]
  • 3
  • [ 17217-57-1 ]
  • C62H50Cl2IrP3 [ No CAS ]
  • [ 3109-63-5 ]
  • [ 7558-02-3 ]
  • C56H47BrIrN2O2P2(1+)*F6P(1-) [ No CAS ]
YieldReaction ConditionsOperation in experiment
43% 4,4?-Dimethoxy-2, 2?-bipyridine (235 mg, 1.09 mmol) and potassium bromide (258 mg, 2.17 mmol) was added to a suspension of 6 (250 mg, 0.217 mmol) in chloroform (40 mL). The mixture was refluxed at 60 °C for 48 h. After cooling, the solution was concentrated to approximately 2 mL under vacuum. Ether (20 mL) was added to the solution to give a yellow precipitate. The filtration was mixed with terabutylammonium hexafluorophosphate (84 mg, 2.17 mmol). Dichloromethane (20 mL) were added and then the mixture was stirred for 2 h. Then the solution was concentrated to approximately 2 mL under vacuum, and ether (20 mL) was added to the solution, yellow precipitate was collected by filtration and chromatographed using CH2Cl2/methanol (100:1 v/v) to afford a yellow solid 4 (119 mg, 43percent).1H NMR (400 MHz, CDCl3): delta=10.0 (d, 3JPH=13.6 Hz, 1 H, IrCH),7.7?8.6 (m, 6 H, bipyridyl), 6.8?7.7 (m, 30 H, PPh3), 5.2?6.5 (m, 4 H,phenyl), 4.1, 4.0 (s, 6 H, OCH3). 31P NMR (162 MHz, CD3CN): delta=11.5(d, J=8.4 Hz, CPPh3), - 9.5 (s, IrPPh3). 13C NMR (101 MHz, CD3CN):delta=193.8 (s, IrCH), 168.3 (d, 2JPC=24.1 Hz, COCH3), 158.1, 157.8,154.6, 151.8 (s, bipyridyl), 152.5 (d, 2JPC=22.4 Hz, IrCHC(PPh3)C),147.8 (dd, 2JPC=12.9 Hz, IrC), 112.6?135.6 (m, PPh3, phenyl, andbipyridyl), 120.3 (d, 1JPC=88.5 Hz, IrCHC(PPh3)), 57.24, 57.20 ppm(s, OCH3). HR-MS: m/z [M]+ calcd for C56H47BrIrN2O2P2+ 1113.1920,found 1113.1915. IR (KBr, cm?1): 835 (P?F). Anal. Calcd forC56H47BrF6IrN2O2P3: C 53.42, H 3.76, N 2.23. Found: C 53.03, H 3.89,N 2.50percent.
  • 4
  • [ 17217-57-1 ]
  • C62H50Cl2IrP3 [ No CAS ]
  • [ 3109-63-5 ]
  • [ 7681-82-5 ]
  • C56H47IIrN2O2P2(1+)*F6P(1-) [ No CAS ]
YieldReaction ConditionsOperation in experiment
26% 4,4?-Dimethoxy-2,2?-bipyridine (188 mg, 0.87 mmol) and sodium iodide (260 mg, 1.74 mmol) was added to a suspension of 6 (200 mg, 0.17 mmol) in chloroform (40 mL). The mixture was refluxed at 60 °C for 48 h. After cooling, the solution was concentrated to approximately 2 mL under vacuum. Ether (20 mL) was added to the solution to give a yellow precipitate. The filtration was mixed with terabutylammonium hexafluorophosphate (673 mg, 1.74 mmol). Dichloromethane (20 mL) were added and then the mixture was stirred for 2 h. Then the solution was concentrated to approximately 2 mL under vacuum, and ether (20 mL) was added to the solution, yellow precipitate was collected by filtration and chromatographed using CH2Cl2/methanol (100:1 v/v) to afford a yellow solid 5 (60 mg, 26percent). 1H NMR (400 MHz, CD3CN): delta=10.0 (d, 3JPH=13.6 Hz, 1 H, IrCH), 7.7?8.8 (m, 6 H, bipyridyl), 6.9?7.7 (m, 30 H, PPh3), 5.0?6.4 (m, 4 H, phenyl), 4.05, 3.99 (s, 6 H,OCH3). 31P NMR (162 MHz, CD2Cl2): delta=11.7 (d, J=8.8 Hz, CPPh3), -8.61 (d, J=9.2 Hz, IrPPh3). 13C NMR (): delta=101 MHz, CD2Cl2194.0 (d, 2JPC=10.0 Hz, IrCH), 169.5 (d, 2JPC=34.8 Hz, COCH3), 159.7,159.2, 156.0, 153.3 (s, bipyridyl), 152.9 (d, 2JPC=20.2 Hz,IrCHC(PPh3)C), 152.1 (dd, 2JPC=63.9 Hz, IrC), 111.6?136.6 (m, PPh3, phenyl, and bipyridyl), 121.7 (d, 1JPC=88.3 Hz, IrCHC(PPh3)), 58.70 ppm (s, OCH3). HR-MS: m/z [M]+ calcd for C56H47IIrN2O2P2+1161.1781, found 1161.1775. IR (KBr, cm?1): 842 (P?F). Anal. Calcdfor C56H47F6IIrN2O2P3: C 51.50, H 3.63, N 2.14. Found: C 50.73, H3.95, N 2.44percent.
 

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