CC BY-NC-ND 4.0 · Organic Materials 2021; 03(02): 141-145
DOI: 10.1055/s-0041-1727093
Focus Issue: Peter Bäuerle 65th Birthday
Short Communication

Boosting the Stability of Boron Peroxides through Subphthalocyanine Coordination

a  Department of Organic Chemistry, Universidad Autónoma de Madrid, Campus de Cantoblanco, 28049, Madrid, Spain
,
Elisa López-Serrano
a  Department of Organic Chemistry, Universidad Autónoma de Madrid, Campus de Cantoblanco, 28049, Madrid, Spain
,
a  Department of Organic Chemistry, Universidad Autónoma de Madrid, Campus de Cantoblanco, 28049, Madrid, Spain
b  Institute of Advanced Research in Chemical Sciences, Universidad Autónoma de Madrid. Campus de Cantoblanco, 28049, Madrid, Spain
c  IMDEA-Nanociencia, C/ Faraday 9, Campus de Cantoblanco, 28049, Madrid, Spain
› Author Affiliations
Funding Information Financial support from Spanish MINECO (CTQ2017-85393-P) is acknowledged. IMDEA Nanociencia acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, Grant SEV2016-0686).


Abstract

The great potential of subphthalocyanines (SubPcs) to stabilize boron peroxides has been demonstrated. In particular, a subphthalocyanato boron (III) peroxide has been prepared in good yield via boron triflate. This derivative is remarkably stable under ambient conditions and can be fully characterized. The impact of the peroxide group on the structural and optoelectronic properties of SubPc was examined by NMR and UV/Vis spectroscopies, as well as single-crystal X-ray diffraction analysis. Moreover, density functional theory calculations were performed to explain the experimental results. The reactivity of this peculiar boron peroxide as an oxidant and a Lewis base was also studied.

Supporting Information

Supporting information for this article is available online at: https://doi.org/10.1055/s-0041-1727093.


Primary Data

The primary data generated during this study are available at: https://doi.org/10.1055/s-0041-1727093.


Dedicated to Professor Peter Bäuerle on the occasion of his 65th Anniversary.


Supporting Information



Publication History

Received: 03 February 2021

Accepted: 24 February 2021

Publication Date:
01 April 2021 (online)

© 2021. The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution-NonDerivative-NonCommercial License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes, or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by-nc-nd/4.0/)

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 
  • References And Notes

  • 1 Brown HC, Zweifel G. J. Am. Chem. Soc. 1959; 81: 247
  • 2 Ollivier C, Renaud P. Chem. Rev. 2001; 101: 3415
    • 3a Wood TK, Piers WE, Keay BA, Parvez M. Angew. Chem. Int. Ed. 2009; 48: 4009
    • 3b Henthorn JT, Agapie T. Angew. Chem. Int. Ed. 2014; 53: 12893
    • 3c Kong L, Lu W, Li Y, Ganguly R, Kinjo R. Angew. Chem. Int. Ed. 2016; 55: 14718
    • 3d Tao X, Daniliuc CG, Janka O, Poettgen R, Knitsch R, Hansen MR, Eckert H, Luebbesmeyer M, Studer A, Kehr G, Erker G. Angew. Chem. Int. Ed. 2017; 56: 16641
    • 4a Clay JM, Vedejs E. J. Am. Chem. Soc. 2005; 127: 5766
    • 4b Salomon MA, Braun T, Penner A. Angew. Chem. Int. Ed. 2008; 47: 8867
    • 4c Baumgarth H, Meier G, von Hahmann CN, Braun T. Dalton Trans. 2018; 47: 16299
  • 5 Adamo C, Amatore C, Ciofini I, Jutand A, Lakmini H. J. Am. Chem. Soc. 2006; 128: 6829
    • 6a Porcel S, Bouhadir G, Saffon N, Maron L, Bourissou D. Angew. Chem. Int. Ed. 2010; 49: 6186
    • 6b Taylor JW, McSkimming A, Guzman CF, Harman WH. J. Am. Chem. Soc. 2017; 139: 11032
    • 6c Wang B, Kinjo R. Chem. Sci. 2019; 10: 2088
  • 7 Tsurumaki E, Sung J, Kim D, Osuka A. Angew. Chem. Int. Ed. 2016; 55: 2596
  • 8 Claessens CG, González-Rodríguez D, Rodríguez-Morgade MS, Medina A, Torres T. Chem. Rev. 2014; 114: 2192
    • 9 See Section 2.5.6. of Ref. 8 and references therein. For examples on SubPc properties, see also:
    • 9a Claessens CG, Gonzalez-Rodriguez D, Torres T, Martin G, Agullo-Lopez F, Ledoux I, Zyss J, Ferro VR, Garcia de la Vega JM. J. Phys. Chem. B. 2005; 109: 3800
    • 9b Verreet B, Rand BP, Cheyns D, Hadipour A, Aernouts T, Heremans P, Medina A, Claessens CG, Torres T. Adv. Energy Mater. 2011; 1: 565
    • 9c Lavarda G, Zirzlmeier J, Gruber M, Rami PR, Tykwinski RR, Torres T, Guldi DM. Angew. Chem., Int. Ed. 2018; 57: 16291
    • 9d Zirzlmeier J, Lavarda G, Gotfredsen H, Papadopoulos I, Chen L, Clark T, Tykwinski RR, Torres T, Guldi DM. Nanoscale 2020; 12: 23061
    • 10a Guilleme J, Martínez-Fernández L, González-Rodríguez D, Corral I, Yáñez M, Torres T. J. Am. Chem. Soc. 2014; 136: 14289
    • 10b Guilleme J, Martínez-Fernández L, Corral I, Yáñez M, González-Rodríguez D, Torres T. Org. Lett. 2015; 17: 4722
  • 11 Guilleme J, Gonzalez-Rodriguez D, Torres T. Angew. Chem. Int. Ed. 2011; 50: 3506
  • 12 Synthetic procedure for t BuOO-SubPcH12: In a 10 mL round-bottomed flask, equipped with a magnetic stirrer and a rubber seal, Cl-SubPcH12 (0.025 mmol) and silver trifluoromethanesulfonate (0.031 mmol; 1.25 equiv) were placed. Anhydrous toluene (3 mL) was added and the mixture was stirred under an argon atmosphere at room temperature until the disappearance of the SubPcCl starting material, which was monitored by TLC. At this point tert-butyl peroxide (5–6 M in decane, 0.031 mmol, 1.25 equiv) and N,N-diisopropylethylamine (0.031 mmol, 1.25 equiv) were added. The reaction mixture was then stirred at 50 °C for 20 min. The residue was purified by column chromatography on silica gel using toluene/AcOEt (5:1) as the eluent. The product obtained from the column was further purified washing with cold hexane. t BuOO-SubPcH12 was isolated as a pink solid in 86%. 1H-NMR (300 MHz, CDCl3): δ ppm = 8.88 (m, 6 H), 7.89 (m, 6 H), 0.34 (s, 9 H). 13C-NMR (75.5 MHz, CDCl3): δ ppm = 151.6, 131.2, 129.8, 122.3, 25.4. 11B-NMR (96 MHz, CDCl3): δ ppm = −13.8. HRLSI-MS (MALDI-TOF): Calculated for C28H21BN6O2: 484.1819; Found: 484.1840. UV/vis (DCM): λmax (nm) (log ε); ΦF (exc. λ = 570 nm) = 0.86; FT-IR: ν (cm −1) = 3062, 2972, 2913, 1613, 1453, 1283, 1128, 1058, 744. Mp > 200 °C
  • 13 Kato T, Tham FS, Boyd PD. W, Reed CA. Heteroat. Chem. 2006; 17: 209
  • 14 To understand the notation of the different arrangements of SubPcs in the solid state, please see Section 2.4.1 of Ref 8
  • 15 Fulford MV, Jaidka D, Paton AS, Morse GE, Brisson ER. L, Lough AJ, Bender TP. J. Chem. Eng. Data 2012; 57: 2756
  • 16 Reduction between −1.58 V and −0.82 V and oxidation between 1.15 V and 0.37 V. See Section 2.3.7 of Ref 8 for further details