Energy conversion and storage via photoinduced polarization change in non-ferroelectric molecular [CoGa] crystals

1.

2.

3.

4.

5.

6.

7.

8.

9.

10.

11.

12.

13.

14.

15.

16.

17.

18.

Emerging Materials for Energy Conversion and Storage (Eds.

Cheong K. Y., Impellizzeri G. & Fraga M. A.) 461–472 (Elsevier, 2018).

Lu, K. Materials in Energy Conversion, Harvesting, and Storage Ch 4

(John Wiley & Sons, Inc., Hoboken, New Jersey, 2014).

Pandya, S. et al. New approach to waste-heat energy harvesting:

pyroelectric energy conversion. NPG Asia Mater. 11, 26 (2019).

Boriskina, S. V. et al. Roadmap on optical energy conversion. J. Opt.

18, 073004 (2016).

Green, M. A. & Bremner, S. P. Energy conversion approaches and

materials for high-efficiency photovoltaics. Nat. Mater. 16,

23–34 (2017).

Green, M. A. Third generation photovoltaics- Advanced Solar

Energy Conversion (Springer Series in Photonics, Springer Berlin,

Heidelberg, 2006).

Saeki, A. Evaluation-oriented exploration of photo energy conversion systems: from fundamental optoelectronics and material

screening to the combination with data science. Polym. J. 52,

1307–1321 (2020).

Nakamura, M. et al. Shift current photovoltaic effect in a ferroelectric charge-transfer complex. Nat. Commun. 8, 281 (2017).

Tan, L. Z. et al. Shift current bulk photovoltaic effect in polar

materials—hybrid and oxide perovskites and beyond. npj Comput.

Mater. 2, 16026 (2016).

Sato, O. Dynamic molecular crystals with switchable physical

properties. Nat. Chem. 8, 644–656 (2016).

Wu, S.-Q. et al. Macroscopic polarization change via electron

transfer in a valence tautomeric cobalt complex. Nat. Commun. 11,

1992 (2020).

Gransbury, G. K. & Boskovic, C. Valence tautomerism in d-block

complexes. Encycl. Inorg. Bioinorg. Chem. 1–24 (2021).

Senthil Kumar, K. & Ruben, M. Emerging trends in spin crossover

(SCO) based functional materials and devices. Coord. Chem. Rev.

346, 176–205 (2017).

Sato, O., Tao, J. & Zhang, Y.-Z. Control of magnetic properties

through external stimuli. Angew. Chem. Int. Ed. 46, 2152–2187

(2007).

Spin-Crossover Materials: Properties and Application (ed. Halcrow,

M. A.) John Wiley & Sons, Ltd, UK, 2013.

Lu, Y.-L., Lan, W.-L., Shi, W., Jin, Q.-H. & Cheng, P. Photo-induced

variation of magnetism in coordination polymers with ligand-based

electron transfer. Dalton Trans. 50, 13124–13137 (2021).

Witt, A., Heinemann, F. W. & Khusniyarov, M. M. Bidirectional photoswitching of magnetic properties at room temperature: liganddriven light-induced valence tautomerism. Chem. Sci. 6, 4599–4609

(2015).

Carbonera, C., Dei, A., Létard, J.-F., Sangregorio, C. & Sorace, L.

Thermally and light-induced valence tautomeric transition in a

dinuclear cobalt–tetraoxolene complex. Angew. Chem. Int. Ed. 43,

3136–3138 (2004).

Nature Communications | (2023)14:3394

https://doi.org/10.1038/s41467-023-39127-8

19. Ash, R., Zhang, K. & Vura-Weis, J. Photoinduced valence tautomerism of a cobalt-dioxolene complex revealed with femtosecond

M-edge XANES. J. Chem. Phys. 151, 104201 (2019).

20. Kanegawa, S. et al. Directional electron transfer in crystals of [CrCo]

dinuclear complexes achieved by chirality-assisted preparative

method. J. Am. Chem. Soc. 138, 14170–14173 (2016).

21. Sadhukhan, P. et al. Manipulating electron redistribution to achieve

electronic pyroelectricity in molecular [FeCo] crystals. Nat. Commun. 12, 4836 (2021).

22. Beni, A. et al. Optically induced valence tautomeric interconversion

in cobalt dioxolene complexes. J. Braz. Chem. Soc. 17, 1522–1533

(2006).

23. Shapovalova, S. O. et al. Temperature and time-resolved XANES

studies of novel valence tautomeric cobalt complex. Chem. Lett.

50, 1933–1937 (2021).

24. Liang, H. W. et al. Charge and spin-state characterization of cobalt

bis(o-dioxolene) valence tautomers using Co Kβ X-ray emission and

L-edge X-ray absorption spectroscopies. Inorg. Chem. 56,

737–747 (2017).

25. Baker, M. L. et al. K- and L-edge X-ray absorption spectroscopy

(XAS) and resonant inelastic X-ray scattering (RIXS) determination

of differential orbital covalency (DOC) of transition metal sites.

Coord. Chem. Rev. 345, 182–208 (2017).

26. Haverkort, M. W., Zwierzycki, M. & Andersen, O. K. Multiplet ligandfield theory using Wannier orbitals. Phys. Rev. B 85, 165113 (2012).

27. Retegan, M. Crispy: v0.7.3 (2019).

28. Gütlich, P., Gaspar, A. B. & Garcia, Y. Spin state switching in iron

coordination compounds. Beilstein J. Org. Chem. 9, 342–391

(2013).

29. Su, S.-Q. et al. Photoinduced persistent polarization change in a

spin transition crystal. Angew. Chem. Int. Ed. 61, e202208771 (2022).

30. Tait, A. M., Busch, D. H. & Curtis, N. F. 5,5,7,12,12,14-hexamethyl

−1,4,8,11-tetraazacyclo-tetradecane (5,5,7,12,12,14-Me6[14]Ane1,4,8,11-N4) complexes. Inorg. Synth. 18, 10–17 (1978).

31. Ito, H., Fujita, J., Toriumi, K. & Ito, T. Optical resolution of rac5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclo-tetradecane (L),

circular dichroism spectra of Ni(II) complexes with the active ligand,

and the absolute configuration of (–)589-[(Ni(SS-L))2(d-tart)(H2O)]

(ClO4)2•2H2O as determined by the X-ray analysis. Bull. Chem. Soc.

Jpn. 54, 2988–2994 (1981).

32. Buchner, M., Höfler, K., Henne, B., Ney, V. & Ney, A. Tutorial: basic

principles, limits of detection, and pitfalls of highly sensitive SQUID

magnetometry for nanomagnetism and spintronics. J. Appl. Phys.

124, 161101 (2018).

33. Lubomirsky, I. & Stafsudd, O. Practical guide for pyroelectric measurements. Rev. Sci. Instrum. 83, 051101 (2012).

Acknowledgements

This work was supported by JSPS KAKENHI Grant Numbers

JP20H00385, JP20K05421, JP21K05085, JP21K05086, JP20K15247. Use

of the Stanford Synchrotron Radiation Lightsource, SLAC National

Accelerator Laboratory, is supported by the U.S. Department of Energy,

Office of Science, Office of Basic Energy Sciences. M.L.B. acknowledges

the support of the Royal Society of Chemistry (RM1802-4019) and the

University of Manchester.

Author contributions

O.S. and S.K. supervised the project. P.S. and T.N. carried out synthetic

and crystallographic experiments. Pyroelectric measurement was performed by P.S., S.-Q.W., S.K., X.Z. and K.G. Light-energy conversion was

measured by P.S. and J.I.L. M.L.B., M.S.H., J.G.C., T.K. and D.S. measured

and analysed the HERFD spectra. R.S., H.O. and A.S. performed the IR

measurements. S.K. and S.-Q.W. have carried out theoretical analysis.

P.S., S.-Q.W., S.-Q.S., S.K. and O.S. discussed and co-wrote the

manuscript.

Article

Competing interests

The authors declare no competing interests.

Additional information

Supplementary information The online version contains

supplementary material available at

https://doi.org/10.1038/s41467-023-39127-8.

Correspondence and requests for materials should be addressed to

Shinji Kanegawa or Osamu Sato.

Peer review information Nature Communications thanks the anonymous reviewers for their contribution to the peer review of this work.

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