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One-dimensional alkylate-bridged Würster’s blue-based diradical dications

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Abstract

By using weakly coordinating anions we succeeded in the stabilization and isolation of two Würster’s blue-based diradicaloid dications with saturated spacers. Their geometries and electronic structures were investigated by various experiments in conjunction with DFT calculations. Both one-dimensional alkylate-bridged dications show considerable diradical character with spacer-dependent singlet-triplet energy gaps. One of them displays a much enhanced diradical character and could basically be viewed as a pure diradical with degeneracy of singlet and triplet states.

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References

  1. Salem L, Rowland C. Angew Chem Int Ed, 1972, 11: 92–111

    Article  CAS  Google Scholar 

  2. Rajca A. Chem Rev, 1994, 94: 871–893

    Article  CAS  Google Scholar 

  3. Abe M, Ye J, Mishima M. Chem Soc Rev, 2012, 41: 3808–3820

    Article  CAS  Google Scholar 

  4. Abe M. Chem Rev, 2013, 113: 7011–7088

    Article  CAS  Google Scholar 

  5. Sun Z, Ye Q, Chi C, Wu J. Chem Soc Rev, 2012, 41: 7857–7889

    Article  CAS  Google Scholar 

  6. Casado J, Ponce Ortiz R, López Navarrete JT. Chem Soc Rev, 2012, 41: 5672–5686

    Article  CAS  Google Scholar 

  7. Bruce CR, Norberg RE, Weissman SI. J Chem Phys, 1956, 24: 473–475

    Article  CAS  Google Scholar 

  8. Duffy Jr. W. J Chem Phys, 1962, 36: 490–493

    Article  CAS  Google Scholar 

  9. Thomas DD, Keller H, McConnell HM. J Chem Phys, 1963, 39: 2321–2329

    Article  CAS  Google Scholar 

  10. Kinoshita M, Akamatu H. Nature, 1965, 207: 291–292

    Article  CAS  Google Scholar 

  11. Monkhorst HJ, Kommandeur J. J Chem Phys, 1967, 47: 391–395

    Article  CAS  Google Scholar 

  12. de Boer JL, Vos A. Acta Crystallogr B, 1972, 28: 835–839

    Article  Google Scholar 

  13. Somoano R, Hadek V, Yen SPS, Rembaum A, Deck R. J Chem Phys, 1975, 62: 1061–1067

    Article  CAS  Google Scholar 

  14. Kaufman FB. J Am Chem Soc, 1976, 98: 5339–5344

    Article  CAS  Google Scholar 

  15. Terauchi H, Sakamoto N, Shirotani I. J Chem Phys, 1976, 64: 437–438

    Article  CAS  Google Scholar 

  16. Iyechika Y, Yakushi K, Kuroda H. Bull Chem Soc Jpn, 1980, 53: 603–610

    Article  CAS  Google Scholar 

  17. Soos ZG. J Chem Phys, 1981, 74: 5287–5294

    Article  CAS  Google Scholar 

  18. Yamauchi J, Fujita H. Bull Chem Soc Jpn, 1990, 63: 2928–2932

    Article  CAS  Google Scholar 

  19. Awano H, Araki H, Ohigashi H. Synth Met, 1993, 55: 685–689

    Article  CAS  Google Scholar 

  20. Colin Baird N, Wang H. Chem Phys Lett, 1993, 202: 501–505

    Article  Google Scholar 

  21. Brouwer AM. J Phys Chem A, 1997, 101: 3626–3633

    Article  CAS  Google Scholar 

  22. Wienk MM, Janssen RAJ. J Am Chem Soc, 1996, 118: 10626–10628

    Article  CAS  Google Scholar 

  23. Wienk MM, Janssen RAJ. J Am Chem Soc, 1997, 119: 4492–4501

    Article  CAS  Google Scholar 

  24. Ito A, Ono Y, Tanaka K. Angew Chem Int Ed, 2000, 39: 1072–1075

    Article  CAS  Google Scholar 

  25. van Meurs PJ, Janssen RAJ. Synth Met, 2001, 121: 1832–1833

    Article  Google Scholar 

  26. Nelsen SF, Li G, Schultz KP, Tran HQ, Guzei IA, Evans DH. J Am Chem Soc, 2008, 130: 11620–11622

    Article  CAS  Google Scholar 

  27. Jalilov AS, Li G, Nelsen SF, Guzei IA, Wu Q. J Am Chem Soc, 2010, 132: 6176–6182

    Article  CAS  Google Scholar 

  28. Jalilov AS, Nelsen SF, Guzei IA, Wu Q. Angew Chem Int Ed, 2011, 50: 6860–6863

    Article  CAS  Google Scholar 

  29. Zalibera M, Jalilov AS, Stoll S, Guzei IA, Gescheidt G, Nelsen SF. J Phys Chem A, 2013, 117: 1439–1448

    Article  CAS  Google Scholar 

  30. Nelsen SF, Yunta MJR. J Phys Org Chem, 1994, 7: 55–62

    Article  CAS  Google Scholar 

  31. Krossing I. Chem Eur J, 2001, 7: 490–502

    Article  CAS  Google Scholar 

  32. X-ray data for 1 2+ and 2 2+ are listed in Table S1 in the Supporting Information. CCDC 1449977–1449978 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif

  33. Ohashi K, Kubo T, Masui T, Yamamoto K, Nakasuji K, Takui T, Kai Y, Murata I. J Am Chem Soc, 1998, 120: 2018–2027

    Article  CAS  Google Scholar 

  34. Bleaney B, Bowers KD. Proc R Soc A-Math Phys Eng Sci, 1952, 214: 451–465

    Article  CAS  Google Scholar 

  35. All calculations were performed using the Gaussian 09 program suite. Frisch MJ, et al. Gaussian 09. Revision B.01. Wallingford, CT: Gaussian, Inc., 2010. See Supporting Information for coordinates and full citation

  36. Nakano M. Excitation Energies and Properties of Open-Shell Singlet Molecules Applications to a New Class of Molecules for Nonlinear Optics and Singlet Fission. New York: Springer, 2014

    Google Scholar 

  37. Kamada K, Fuku-en S, Minamide S, Ohta K, Kishi R, Nakano M, Matsuzaki H, Okamoto H, Higashikawa H, Inoue K, Kojima S, Yamamoto Y. J Am Chem Soc, 2013, 135: 232–241

    Article  CAS  Google Scholar 

  38. Bonness S, Fukui H, Yoneda K, Kishi R, Champagne B, Botek E, Nakano M. Chem Phys Lett, 2010, 493: 195–199

    Article  CAS  Google Scholar 

  39. Muhammad S, Fukuda K, Minami T, Kishi R, Shigeta Y, Nakano M. Chem Eur J, 2013, 19: 1677–1685

    Article  CAS  Google Scholar 

  40. Muhammad S, Ito S, Nakano M, Kishi R, Yoneda K, Kitagawa Y, Shkir M, Irfan A, Chaudhry AR, AlFaify S, Kalam A, Al-Sehemi AG. Phys Chem Chem Phys, 2015, 17: 5805–5816

    Article  CAS  Google Scholar 

  41. Barlow S, Risko C, Chung SJ, Tucker NM, Coropceanu V, Jones SC, Levi Z, Brédas JL, Marder SR. J Am Chem Soc, 2005, 127: 16900–16911

    Article  CAS  Google Scholar 

  42. Barlow S, Risko C, Odom SA, Zheng S, Coropceanu V, Beverina L, Brédas JL, Marder SR. J Am Chem Soc, 2012, 134: 10146–10155

    Article  CAS  Google Scholar 

  43. Wang X, Zhang Z, Song Y, Su Y, Wang X. Chem Commun, 2015, 51: 11822–11825

    Article  CAS  Google Scholar 

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Acknowledgments

This work was supported by the National Natural Science Foundation of China (21525102, 2169002) and the Natural Science Foundation of Jiangsu Province (BK20140014). We are thankful to Dr. Xingyong Wang for the writing of the first draft.

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Authors and Affiliations

  1. State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering; Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing, 210093, China

    Tao Li, Houjia Wei, Yue Zhao, Yunxia Sui & Xinping Wang

  2. School of Chemistry and Chemical Engineering, Huaiyin Normal University, Huai’an, 223300, China

    Zaichao Zhang

Authors
  1. Tao Li
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  2. Houjia Wei
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  3. Zaichao Zhang
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  4. Yue Zhao
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  5. Yunxia Sui
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  6. Xinping Wang
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Correspondence to Xinping Wang.

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Li, T., Wei, H., Zhang, Z. et al. One-dimensional alkylate-bridged Würster’s blue-based diradical dications. Sci. China Chem. 60, 602–606 (2017). https://doi.org/10.1007/s11426-016-0429-4

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  • DOI: https://doi.org/10.1007/s11426-016-0429-4

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