Dalton Transactions
Communication
= 14 K. The temperature dependence of the ac magnetic sus-
ceptibilities at different frequencies (Fig. S17c†) exhibits the
characteristic peaks with an AF at TN = 14 K in both in-phase
(χ′m) and the out-of-phase (χ″m) parts.
Notes and references
1 R. M. Hazen, T. R. Filley and G. A. Goodfriend, Proc. Natl.
Acad. Sci. U. S. A., 2001, 98, 5487–5490.
The magnetic properties of 2 and 3 were also examined and
are shown in Fig. S11 and S14–S17.† The plots for χmT versus T
indicate that both have AF interactions between Mn(III) ions in
the chain with the fitted data as follows: J = −4.59 cm−1, g =
1.97, zJ′ = −0.055 cm−1 for 2 and J = −3.87 cm−1, g = 1.88, zJ′ =
−0.020 cm−1 for 3. The fitted data of 1–4 indicate that the
smaller the ∠Mn–Oamide–C and the shorter the intrachain Mn
distances (Table S2†), the stronger the AF interaction between
Mn(III) ions. Magnetic hysteresis loops indicate weak ferromag-
netism: the coercive fields are 1.4 (2) and 0.9 kOe (3); the
remnant magnetisations are 0.011 (2) and 0.009Nβ mol−1 (3).
The canting angles (α) of 2 and 3 are 0.32 and 0.24°, respect-
ively. The temperature of phase transitions (TN) confirmed by
ZFC and FC magnetisation are 8 K for 2 and 7 K for 3. The
temperature dependence of ac magnetic susceptibilities of 2
2 (a) R. Noyori, Angew. Chem., Int. Ed., 2002, 41, 2008–2022;
(b) J.-C. Wang, X. Kan, J.-Y. Shang, H. Qiao and Y.-B. Dong,
J. Am. Chem. Soc., 2020, 142, 16915–16920.
3 J. S. Seo, D. Whang, H. Lee, S. I. Jun, J. Oh, Y. J. Jeon and
K. Kim, Nature, 2000, 404, 982–986.
4 D. F. Eaton, Science, 1991, 253, 281–287.
5 X. Zhang, J. Yin and J. Yoon, Chem. Rev., 2014, 114, 4918–
4959.
6 L. Pasteur, C. R. Acad. Sci., 1848, 26, 535–539.
7 A. Collet, M. J. Brienne and J. Jacques, Chem. Rev., 1980, 80,
215–230.
8 J. Jacques, A. Collet and S. H. Wilen, Enantiomers,
Racemates, Resolution, John Wiley & Sons, New York, 1981.
9 T. Ezuhara, K. Endo and Y. Aoyama, J. Am. Chem. Soc.,
1999, 121, 3279–3283.
and 3 (Fig. S17†) shows the peak of an AF at each TN, where 10 J. Szurgot and M. Szurgot, Cryst. Res. Technol., 1995, 30, 71–
the χ′m reaches a maximum, while no obvious χ″m was 79.
observed. Thus, 2 and 3 may be hidden weak ferromagnets 11 C. Viedma, Phys. Rev. Lett., 2005, 94, 065504.
due to spin canting.29 These detailed investigations show that 12 (a) A. Maity, M. Gangopadhyay, A. Basu, S. Aute, S. S. Babu
the magnetism of each compound depends on the separation
of Mn(III) ions, both intra- and inter-1D chain, modulated by
the halogen substituents so as to control the bulk magnetic
properties.
In summary, all the compounds described herein crystallise
as unbalanced conglomerates of chiral crystals even though
and A. Das, J. Am. Chem. Soc., 2016, 138, 11113–11116;
(b) I. Bernal and R. A. Lalancette, C. R. Chim., 2015, 18,
929–934; (c) I. Bernal, J. Cai, S. S. Massoud, S. F. Watkins
and F. Fronczek, J. Coord. Chem., 1996, 38, 165;
(d) I. Bernal, F. Somoza and V. Bahn, J. Coord. Chem., 1997,
42, 1.
the constituent complexes are all achiral. The chirality of the 13 S.-W. Cheong and M. Mostovoy, Nat. Mater., 2007,
individual crystals reflects the presence of helical coordination 6, 13.
polymer units of one chirality associated with one chirality of 14 C. Train, R. Gheorghe, V. Krstic, L.-M. Chamoreau,
the central chelate rings, M helices being associated with δ
conformations or P with λ in all cases. The chiral environment
N. S. Ovanesyan, G. L. J. A. Rikken, M. Gruselle and
M. Verdaguer, Nat. Mater., 2008, 7, 729–734.
imposed on the Mn(III) centers renders them dissymmetric, 15 S. Kusumoto, A. Koga, F. Kobayashi, R. Ohtani, Y. Kim,
leading to appreciable circular dichroism of the d–d bands in
the solid state. Although enantiomeric excesses in the bulk
L. F. Lindoy, S. Hayami and M. Nakamura, Dalton Trans.,
2019, 48, 8617–8622.
products vary, in all cases there is symmetry breaking in crys- 16 R. D. Gillard, The Cotton Effect in Coordination Compounds,
tallisation of a nature which depends on the ligand substitu-
in Progress in Inorganic Chemistry, ed. F. A. Cotton, John
ents. In complex 4 in particular, crystals containing the P helix
Wiley & Sons, Inc., USA, 1967, vol. 7.
of the coordination polymer always appear to predominate. 17 I. Bernal, J. Chem. Educ., 1992, 69, 468.
The change of substituents (Cl, Br and I) on the coordinated 18 M. Matsushima, K. Wada, Y. Horino, K. Takahara,
ligand significantly influences the magnetic properties, with
coercive fields of 0.9–10 kOe, that of 4 being the highest
known for Mn(III) complexes exhibiting weak ferromagnetism.
Y. Sunatsuki and T. Suzuki, CrystEngComm, 2020, 22, 458–
466.
19 C. Viedma, Cryst. Growth Des., 2007, 7, 553–556.
20 V. Marichez, A. Tassoni, R. P. Cameron, S. M. Barnett,
R. Eichhorn, C. Genet and T. M. Hermans, Soft Matter,
2019, 15, 4593–4608.
Conflicts of interest
21 K. Suwannasang, A. E. Flood, C. Rougeot and G. Coquerel,
Cryst. Growth Des., 2013, 13, 3498–3504.
There are no conflicts to declare.
22 D. K. Kondepudi, J. Laudadio and K. Asakura, J. Am. Chem.
Soc., 1999, 121, 1448–1451.
23 (a) W. Meyerhoffer, Chem. Ber., 1904, 37, 2604–2610;
(b) C. Viedma, B. J. V. Verkuijl, J. E. Ortiz, T. d. Torres,
R. M. Kellogg and D. G. Blackmond, Chem. – Eur. J., 2010,
16, 4932–4937.
Acknowledgements
This work was supported by KAKENHI Grant-in-Aid for
Scientific Research (A) JP17H01200.
This journal is © The Royal Society of Chemistry 2021
Dalton Trans., 2021, 50, 5428–5432 | 5431