Tris(pentafluorophenyl)corrolatoindium(III) – A Long-awaited Metallocorrole: Synthesis and Characterization

Abstract

The first attempts at the synthesis of an indium corrole compound were synthesized in the late 80s, but it has not been possible to obtain and characterize such complex completely, and the indium part of metallocorrole’s periodic table remained unfilled. In this work, an efficient insertion of indium into the 5,10,15-tris(pentafluorophenyl)corrole was achieved. The obtained 5,10,15-tris(pentafluorophenyl)corrolato indium(III) derivatives has been successfully characterized by relevant analytical techniques and some photophysical and electrochemical features were studied and investigated for the first time. As a novel research, 19F-19F COSY NMR technique was employed for the first time in corrole chemistry and the obtained results were further compared to the geometry-optimized molecular structure via density functional theory (DFT) calculations.

Keywords

• corrole
• indium
• metallocorrole
• NMR
• 19F-19F COSY

Supporting Institution

Academy of Finland

Project Number

Funding Decision Number 334828

Thanks

We would like to thank to the Academy of Finland (Suomen Akatemia, Funding Decision Number 334828), University of Turku (UTU) and the École Polytechnique Fédérale de Lausanne (EPFL) to support our PhD student, Ali Tuna for his projects. We would also like to thank Dr. Jeremy Weaver, University of Wisconsin – Madison, USA) who carried out his PhD thesis on the investigation of indium corrole formation and discussions, and NMR specialists Aurélien Bornet (EPFL, Switzerland) and Jani Rahkila (Bruker, Finland) for establishing 19F-19F COSY NMR technique for detailed analytical characterization, and Dr. Ian Pompermayer Machado (UTU, Finland) for fluorescence spectroscopy measurements.

References

1. 1. Kadish K, Smith KM, Guilard R. The Porphyrin Handbook. New York, USA: Academic Press; 1999.
2. 2. Nardis S, Mandoj F, Stefanelli M, Paolesse R. Metal complexes of corrole. Coord Chem Rev [Internet]. 2019 Jun 1;388:360–405. Available from: .
3. 3. Mahammed A, Gross Z. Milestones and Most Recent Advances in Corrole’s Science and Technology. J Am Chem Soc [Internet]. 2023 Jun 14;145(23):12429–45. Available from: .
4. 4. Paolesse R, Licoccia S, Boschi T. Towards the periodic table of metallocorrolates: synthesis and characterization of main group metal complexes of octamethylcorrole. Inorganica Chim Acta [Internet]. 1990 Dec 3;178(1):9–12. Available from: .
5. 5. Orłowski R, Gryko D, Gryko DT. Synthesis of Corroles and Their Heteroanalogs. Chem Rev [Internet]. 2017 Feb 22;117(4):3102–37. Available from: .
6. 6. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, et al. Gaussian 16, Revision C. 01. Wallingford, CT: Gaussian, Inc.; 2016.
7. 7. Becke AD. Density-functional thermochemistry. III. The role of exact exchange. J Chem Phys [Internet]. 1993 Apr 1;98(7):5648–52. Available from: .
8. 8. McLean AD, Chandler GS. Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z =11–18. J Chem Phys [Internet]. 1980 May 15;72(10):5639–48. Available from: .

9. 9. Tomasi J, Mennucci B, Cammi R. Quantum Mechanical Continuum Solvation Models. Chem Rev [Internet]. 2005 Aug 1;105(8):2999–3094. Available from: .
10. 10. Reed AE, Curtiss LA, Weinhold F. Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint. Chem Rev [Internet]. 1988 Sep 1;88(6):899–926. Available from: .
11. 11. Kowalska D, Liu X, Tripathy U, Mahammed A, Gross Z, Hirayama S, et al. Ground- and Excited-State Dynamics of Aluminum and Gallium Corroles. Inorg Chem [Internet]. 2009 Mar 16;48(6):2670–6. Available from: .
12. 12. Reith LM, Stiftinger M, Monkowius U, Knör G, Schoefberger W. Synthesis and Characterization of a Stable Bismuth(III) A 3 –Corrole. Inorg Chem [Internet]. 2011 Jul 18;50(14):6788–97. Available from: .
13. 13. Shen J, Ou Z, Shao J, Gałęzowski M, Gryko DT, Kadish KM. Free-base corroles: determination of deprotonation constants in non-aqueous media. J Porphyr Phthalocyanines [Internet]. 2007 Apr 25;11(04):269–76. Available from: .
14. 14. Weaver J. Corroles [PhD Thesis]. [California, USA]: Technical University of California; 2005.
15. 15. McGarvey BR, Trudell CO, Tuck DG, Victoriano L. Coordination compounds of indium. 37. Indium-115 NMR studies of anionic indium species in nonaqueous solution. Inorg Chem [Internet]. 1980 Nov 1;19(11):3432–6. Available from: .
16. 16. NMR Lab [Internet]. 2023 [cited 2024 Jan 23]. NMR Lab. Available from: .
17. 17. Ward AL, Buckley HL, Lukens WW, Arnold J. Synthesis and Characterization of Thorium(IV) and Uranium(IV) Corrole Complexes. J Am Chem Soc [Internet]. 2013 Sep 18;135(37):13965–71. Available from: .
18. 18. Ziegler JA, Buckley HL, Arnold J. Synthesis and reactivity of tantalum corrole complexes. Dalton Trans [Internet]. 2017 Jan 17;46(3):780–5. Available from: .
19. 19. Vazquez-Lima H, Conradie J, Johansen MAL, Martinsen SR, Alemayehu AB, Ghosh A. Heavy-element–ligand covalence: ligand noninnocence in molybdenum and tungsten Viking-helmet Corroles. Dalt Trans [Internet]. 2021 Sep 28;50(37):12843–9. Available from: .
20. 20. Knör G. Photocatalytic reactions of porphyrin-based multielectron transfer sensitizers. Coord Chem Rev [Internet]. 1998 Apr 1;171:61–70. Available from: .
21. 21. Schöfberger W, Lengwin F, Reith LM, List M, Knör G. Lead corrole complexes in solution: Powerful multielectron transfer reagents for redox catalysis. Inorg Chem Commun [Internet]. 2010 Oct 1;13(10):1187–90. Available from: .
22. 22. Fang Y, Ou Z, Kadish KM. Electrochemistry of Corroles in Nonaqueous Media. Chem Rev [Internet]. 2017 Feb 22;117(4):3377–419. Available from: .
23. 23. Mahammed A, Gross Z. Corroles as triplet photosensitizers. Coord Chem Rev [Internet]. 2019 Jan 15;379:121–32. Available from: .
24. 24. Tuck DG. The lower oxidation states of indium. Chem Soc Rev [Internet]. 1993 Jan 1;22(4):269. Available from: .
25. 25. Hill MS, Hitchcock PB, Pongtavornpinyo R. Oxidative Addition Reactions of Alkyl Halides with the Group 13 Carbene Analogue [In{N(Dipp)C(Me)} 2 CH] (Dipp = 2,6- i Pr 2 C 6 H 3 ). Inorg Chem [Internet]. 2007 Apr 30;46(9):3783–8. Available from: .
26. 26. Hill MS, Hitchcock PB. A mononuclear indium(i) carbene analogue. Chem Commun [Internet]. 2004 Aug 9;2004(16):1818–919. Available from: .
27. 27. Cramer SD, Covino BS, editors. Electrochemical Series. In: Corrosion: Materials [Internet]. ASM International; 2005. p. 665–71. Available from: .