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Chemical Structure| 1148-79-4 Chemical Structure| 1148-79-4

Structure of 2,2':6',2''-Terpyridine
CAS No.: 1148-79-4

Chemical Structure| 1148-79-4

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Kessinger, Matthew ; Whittemore, Thomas ; Grandi, Silvia ; Danilov, Evgeny ; Caramori, Stefano ; Castellano, Felix , et al.

Abstract: Proton-coupled electron transfer (PCET) reactions play a crucial role in the interconversion of metal-aqua and metal-hydroxo species present in transition metal complexes and oxide surfaces (M III -OH + e + H+ → MII -OH2). For ruthenium-based water oxidation catalysts, PCET reactions involved in the mechanism of O2 evolution have demonstrated a strong dependence on the identity and concentration of the proton donor and acceptor with significant rate enhancements observed for electrocatalysis performed in acetate, phosphate, and borate buffered electrolytes. However, the systematic study of this phenomenon has been hampered by the inability to independently measure discrete rates for electron transfer (ET) and proton transfer (PT) under electrochemical applied potentials. Herein, the PCET kinetics and mechanism of metal aqua bond formation in a ruthenium water oxidation catalyst [RuII(tpy)(bpy′)H2O]2+, RuII−OH2 where tpy is and bpy′ is 4,4′-diaminopropylsilatrane-2,2′-bypyridine were investigated at a conductive metal oxide interface as a function of buffer identity and concentration. The reaction of interest was triggered by visible light excitation of the catalyst and the kinetics of the independent ET and PT steps of the PCET mechanism were determined through nanosecond transient absorption spectroscopy. Kinetic measurements performed in aqueous acetate, phosphate, or borate buffer solutions revealed two distinct regimes of PT kinetics solely dependent on the buffer concentration. At the greatest buffer concentrations investigated (2 M acetate) spectral signals corresponding to the discreet ET and PT steps were absent indicative in a change in underlying PCET mechanism. Likewise, kinetic modeling indicated that PT from protonated acetate or phosphate occurred with rate constants that were 2- 4 orders of magnitude greater than those for bulk water. In all, these results suggest that the presence of buffer-bases can significantly enhance PCET rates and, in this reaction, may alter the underlying mechanism.

Keywords: Proton-coupled electron transfer ; transient absorption ; spectroscopy ; kinetics ; mechanism ; interfaces

Purchased from AmBeed:

Kessinger, Matthew ; Soudackov, Alexander V. ; Schneider, Jenny ; Bangle, Rachel E. ; Hammes-Schiffer, Sharon ; Meyer, Gerald J.

Abstract: The reorganization energy (λ) for interfacial electron transfer (ET) and proton-coupled ET (PCET) from a conductive metal oxide (In2O3:Sn, ITO) to a surface-bound H2O oxidation catalyst was extracted from kinetic data measured as a function of the thermodn. driving force. Visible light excitation resulted in rapid excited-state injection (kinj > 108 s-1) to the ITO, which photo-initiated the two interfacial reactions of interest. The rate constants for both reactions increased with the driving force, -ΔG°, to a saturating limit, kmax, with rate constants consistently larger for ET than for PCET. Marcus-Gerischer anal. of the kinetic data provided the reorganization energy for interfacial PCET (0.90 ± 0.02 eV) and ET (0.40 ± 0.02 eV), resp. The magnitude of kmax for PCET decreases with pH, behavior that was absent for ET. Both the decrease in kmax and the larger reorganization energy for an unwanted competing PCET reaction from the ITO to the oxidized catalyst showcases a significant kinetic advantage for driving solar H2O oxidation at high pH. Computational anal. revealed a larger inner-sphere reorganization energy contribution for PCET than for ET arising from a more significant change in the Ru-O bond length for the PCET reaction. Extending the Marcus-Gerischer theory to PCET by including the excited electron-proton vibronic states and the proton donor-acceptor motion provided an apparent reorganization energy of 1.01 eV. The Marcus-Gerischer theory initially developed for ET can be reliably extended to PCET for quantifying and interpreting reorganization energies observed exptl.

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Alternative Products

Product Details of [ 1148-79-4 ]

CAS No. :1148-79-4
Formula : C15H11N3
M.W : 233.27
SMILES Code : C1=CN=C(C=C1)C1=CC=CC(=N1)C1=NC=CC=C1
MDL No. :MFCD00006213
InChI Key :DRGAZIDRYFYHIJ-UHFFFAOYSA-N
Pubchem ID :70848

Safety of [ 1148-79-4 ]

GHS Pictogram:
Signal Word:Danger
Hazard Statements:H300+H310-H315-H319
Precautionary Statements:P501-P270-P262-P264-P280-P337+P313-P305+P351+P338-P361+P364-P332+P313-P301+P310+P330-P302+P352+P310-P405
Class:6.1
UN#:2811
Packing Group:

Computational Chemistry of [ 1148-79-4 ] Show Less

Physicochemical Properties

Num. heavy atoms 18
Num. arom. heavy atoms 18
Fraction Csp3 0.0
Num. rotatable bonds 2
Num. H-bond acceptors 3.0
Num. H-bond donors 0.0
Molar Refractivity 70.7
TPSA ?

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

38.67 Ų

Lipophilicity

Log Po/w (iLOGP)?

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

2.65
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

1.96
Log Po/w (WLOGP)?

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

3.21
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.

1.16
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

3.47
Consensus Log Po/w?

Consensus Log Po/w: Average of all five predictions

2.49

Water Solubility

Log S (ESOL):?

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

-3.13
Solubility 0.173 mg/ml ; 0.000743 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.

-2.4
Solubility 0.935 mg/ml ; 0.00401 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

-6.32
Solubility 0.000111 mg/ml ; 0.000000478 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

High
BBB permeant?

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

Yes
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

Yes
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

Yes
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

Yes
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

Yes
Log Kp (skin permeation)?

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

-6.33 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

0.0
Egan?

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

0.0
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

0.0 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<1.0
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)

2.2

Application In Synthesis of [ 1148-79-4 ]

* 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.

  • Upstream synthesis route of [ 1148-79-4 ]
  • Downstream synthetic route of [ 1148-79-4 ]

[ 1148-79-4 ] Synthesis Path-Upstream   1~1

  • 1
  • [ 1148-79-4 ]
  • [ 148-24-3 ]
  • [ 6046-93-1 ]
  • [ 10380-28-6 ]
  • [ 443913-66-4 ]
References: [1] Dalton Transactions, 2017, vol. 46, # 44, p. 15330 - 15339.
 

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