# Electron diffraction unveils the 2D metal-radical framework of two molecule-based magnets

Emre Yörük, Constance Lecourt, Dominique Housset, Yuuta Izumi, Wai Li Ling, Stéphanie Kodjikian, Evgeny Tretyakov, Katsuya Inoue, Kseniya Maryunina, Cédric Desroches, et al.

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Emre Yörük, Constance Lecourt, Dominique Housset, Yuuta Izumi, Wai Li Ling, et al. Electron diffraction unveils the 2D metal-radical framework of two molecule-based magnets. Inorganic Chemistry Frontiers, 2025, 12, pp.328-341. 10.1039/D4QI02257B. hal-04817945

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This article can be cited before page numbers have been issued, to do this please use: E. Yörük, C. Lecourt, D. Housset, Y. Izumi, D. Luneau, W. L. Ling, S. Kodjikian, E. V. Tretyakov, K. Inoue, K. Maryunina, C. Desroches and H. Klein, *Inorg. Chem. Front.*, 2024, DOI: 10.1039/D4QI02257B.

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# Electron diffraction unveils the 2D metal-radical framework of two molecule-based magnets.

Emre Yörük,ᵇ Constance Lecourt,ª Dominique Housset,ᶜ Yuuta Izumi,ᵈ Wai Li Ling,ᶜ Stéphanie Kodjikian,ᵇ Evgeny Tretyakov,ᶜ Katsuya Inoue,ᵈ Kseniya Maryunina,ᵈ Cédric Desroches,ª Holger Klein,ᵇ Dominique Luneau*ª

## Author Affiliations

a) Laboratoire des Multimatériaux et Interfaces (UMR 5615), Université Claude Bernard Lyon 1,
69100 Villeurbanne, France E-mail: dominique.luneau@univ-lyon1.fr

b) Université Grenoble Alpes and CNRS, Institut Néel, Grenoble, France.

c) Université Grenoble Alpes, CEA, CNRS, IBS, 38000 Grenoble, France.

d) WPI-SKCM², CResCent and Department of Chemistry, Hiroshima University, Kagamiyama-1-3-1, Higashihiroshima, Hiroshima, 739-8526, Japan

e) N. D. Zelinsky Institute of Organic Chemistry, Leninsky Avenue 47, Moscow 119991, Russian Federation
Abstract

Low-dose electron diffraction has been instrumental in determining the crystal structures of two compounds with metal-radical coordination frameworks {[Mn<sup>II</sup><sub>2</sub>(NITIm)<sub>3</sub>]CF<sub>3</sub>SO<sub>3</sub>.CH<sub>3</sub>OH}n (1) and {[Mn<sup>II</sup><sub>2</sub>(NITImMe<sub>2</sub>)<sub>3</sub>]ClO<sub>4</sub>}n (2) that could never be grown to a crystal size large enough for single-crystal X-ray diffraction characterization. The compounds crystallize as nanocrystals upon addition of triflate (1) and perchlorate (2) anions and coordination of manganese(II) with bis-chelate nitronyl nitroxide radicals NITImH (1) and NITImHMe<sub>2</sub> (2) which are respectively 2-(2-imidazolyl)- and 2-(4,5-dimethylimidazol-2-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-3-oxide-1-oxyl. The two compounds have layered crystal structures in which cationic 2D metal-radical coordination polymers {[Mn<sup>II</sup><sub>2</sub>(NITIm)<sub>3</sub>]<sup>+</sup>}n (1) and {[Mn<sup>II</sup><sub>2</sub>(NITImMe<sub>2</sub>)<sub>3</sub>]<sup>+</sup>}n (2) are separated by layers of triflate (1) or perchlorate (2) anions. Magnetic measurements evidence a ferrimagnetic behavior within the 2D metal-radical sheets due to alternating antiferromagnetically coupled spins (S<sub>Mn</sub><sup>2+</sup> = 5/2 and S<sub>radical</sub> = 1/2). Both compounds exhibit a long-range 3D ordering of weak-ferromagnetic type due to spin canting with Curie temperatures T<sub>c</sub> = 45 K (1) and 40 K (2).

This is associated with a field-induced metamagnetic transition from antiferromagnetic to
ferromagnetic coupling of 2D metal-radical sheets. Studies of the crystal structures allows to
rationalize how the molecular structure of nitronyl nitroxide radicals and of the counter-anions
along with crystal packing affect the magnetic behavior related to interlayer distance and
framework flexibility. These results are striking evidence that electron crystallography is a unique
tool to solve structures of metal-organic compounds crystallizing as nanocrystals even with nitronyl
nitroxide radical components too sensitive to typical electron doses. Overcoming the crystal size
barrier, it allows the validation of chemical synthesis and the establishment of magneto-structural
relationships fostering new advances in the design of molecule-based magnets.
Introduction

Molecule-based magnet exploration was initiated nearly forty years ago fostering the design of supramolecular assemblies of open-shell molecules that hold an overall magnetization in the solid state.¹, ²⁻¹¹ They may be purely organic, organometallic charge-transfer or coordination compounds.¹² So far, most fruitful development has relied on coordination chemistry, thanks to a wide variety of paramagnetic centers comprising metal ions and radical ligands when the directionality of the metal-ligand bonds facilitates a better control of the atom arrangement and magnetic interactions among spin carriers.¹, ¹³ Along with this approach, the building of coordination polymers favors the emergence of a network of magnetic exchange interactions among the spin carriers while a gain in the long-range magnetic ordering temperature is expected with increasing the coordination polymer dimensionality *i.e.* formation of 1D (chain), 2D (layered) and 3D metal-organic frameworks. Clearly, crystal structure is a prerequisite to check the supramolecular assemblies as well as for the systematic study of magnetic-structural relationships, and a key factor on controlling functional properties. The difficulty and often impossibility for most compounds with 2D and 3D metal-organic frameworks to grow single crystals large enough for X-ray crystallography (>$10^3$ µm³) has pushed scientists in the field to essentially focus on magnetic single-molecules (0D). This has resulted in significant successes in the design of single-molecule and single-ion magnets¹⁴ and the control of their ground spin state, but in the meantime investigations of metal-organic materials with 3D magnetic ordering has stagnated.
<figure><img src="image_4.png" /><figcaption>**Figure 1:** Schematic representation of nitronyl nitroxide radicals substituted with imidazole (NITImH), 4,5-dimethylimidazole (NITImHMe₂), and benzimidazole (NITBzImH).</figcaption></figure>

The crystal-size barrier has also hampered our investigations of molecular magnets based on the metal-radical approach.² We have previously designed imidazole-substituted derivatives of nitronyl nitroxide radicals (Figure 1) that can coordinate with almost any 3d and 4f metal ion.¹⁵ Furthermore, following deprotonation of the imidazole moiety they become *bis*-chelating bridging ligands that allow the formation of metal-radical coordination polymers. Over the years and repeated attempts, we have succeeded in obtaining single crystals for several compounds that have 1D (chain) and 2D (layered) metal-radical frameworks, enabling us to determine their crystal structures by X-ray diffraction and to study their magneto-structural relationships.¹⁶⁻¹⁸ However, this has only been achieved for a small number of compounds, specifically with Mn²⁺ ions, while the crystal structure of many others could not be elucidated because the crystal sizes were too small for X-ray diffraction experiments, even with synchrotron radiation sources.

Among the few compounds whose crystal structures could be elucidated, most are composed of 2D layered Mn-radical frameworks in which the Mn²⁺ and nitroxide spins are antiferromagnetically coupled. Remarkably and despite these similarities, different types of magnetic behavior are observed which depend on the substituents present on the nitronyl nitroxide radical or on the
counter-anions that intercalate in-between the 2D Mn-radical sheets. Thus, {[Mn<sup>II</sup><sub>2</sub>(NITBzIm)<sub>3</sub>]X}n coordination compounds based on benzimidazole-substituted radical NITBzImH (2-(2-benzimidazolyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-3-oxide-1-oxyl, Figure 1c) with the counter-anions X being either ClO<sub>4</sub><sup>-</sup> (3) or alkylsulfonate<sup>18</sup>, exhibit long-range magnetic ordering. The highest Curie temperature (T<sub>c</sub> = 55 K) has been observed for {[Mn<sup>II</sup><sub>2</sub>(NITBzIm)<sub>3</sub>]ClO<sub>4</sub>}n (3) with perchlorate anions. In contrast, changing the nitronyl nitroxide radical substituent from BzImH to imidazole (ImH) (Figure 1a), led to a series of compounds with structurally similar 2D-coordination frameworks {[Mn<sup>II</sup><sub>2</sub>(NITIm)<sub>3</sub>]X}n (X= ClO<sub>4</sub><sup>-</sup> (4), BF<sub>4</sub><sup>-</sup> (5) and PF<sub>6</sub><sup>-</sup> (6)) but who undergo thermally-induced valence tautomeric (VT) conversions instead.<sup>17, 19, 20</sup> For each of the three compounds, temperature-dependent oxidation states are observed. There is a high temperature region where all manganese ions are in the +II oxidation state and are coordinated by three NITIm<sup>-</sup> anion-radicals. Upon cooling, they oxidize to the +III state, while electrons are transferred to the radicals to reach a low temperature region where two third of radicals are reduced (NITIm<sub>red</sub><sup>2-</sup>) for charge equilibrium, and only one third are still persistent (NITIm<sup>-</sup>). Therefore, the compounds are better formulated as [Mn<sup>II</sup><sub>2-y</sub>Mn<sup>III</sup><sub>y</sub>(NITIm)<sub>3-y</sub>(NITIm<sub>red</sub>)<sub>y</sub>]X}n where y can take any value between 0 and 2 when going from the high to the low temperature regions. The extent of the high and low temperature regions, the smoothness of conversion and the number of steps in between the two regions depend on the counter-anions interlayering the 2D manganese(II)-nitroxide sheets.

These previous studies have led us to consider the distance between the mean planes of the 2D metal-radical frameworks {[Mn<sup>II</sup><sub>2</sub>(radical)<sub>3</sub>]}n sheets as a key parameter in determining whether the compounds undergo long-range magnetic ordering or exhibit VT conversion. To test these assumptions, we investigated here two different structural modifications of {[Mn<sup>II</sup><sub>2</sub>(NITIm)<sub>3</sub>]ClO<sub>4</sub>}n
(4). In compound 1 perchlorate was substituted by the bulkier triflate anion while keeping the same radical derivative NITImH. In compound 2 the size of nitroxide radical was increased by adding two methyl substituents on the imidazole ring to give NITImHMe₂ (Figure 1b),²¹ while keeping the perchlorate anions. Despite numerous attempts, only powders of nano-sized crystals were obtained for compounds 1 and 2 preventing structure determination by single crystal X-ray diffraction. Moreover, our attempts to use powder X-ray diffraction failed to provide a reliable crystal structure, even when the structural motif [Mn¹¹₂(NITIm)₃] from the crystal structure of 4 was used as a reference building block.

Because compounds 1 and 2 could never be grown to a crystal size large enough for single-crystal X-ray diffraction characterization we overcome the crystal size barrier by using electron diffraction (ED) to determine their crystal structures. In the last two decades there have been tremendous methodological advances in the ED technique, based on possibilities of recording quasi-kinematical diffraction intensities via 3D electron diffraction (3D ED) ²², ²³ together with the development of fast hybrid detectors enabling low dose continuous rotation ED data collection.²⁴ These developments have significantly facilitated the structure determination of nanocrystalline samples in material science and chemistry.²⁵⁻²⁷ This has particularly been useful for metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) that often crystallize in the form of nanocrystalline powders.²⁸⁻³³ Moreover, use of low-dose electrons and cryogenic conditions has allowed to minimize electron beam damage on MOFs.³⁴⁻⁴² These advances in 3D ED should benefit to coordination chemists, particularly in the field of molecule-based magnets for which obtaining crystals suitable for X-ray crystallography may be difficult.

Here, we show how ED was successful in determining the crystal structure of two novel magnetic compounds with 2D metal-radical coordination frameworks
`{[Mn<sup>II</sup><sub>2</sub>(NITIm)<sub>3</sub>]CF<sub>3</sub>SO<sub>3</sub>·CH<sub>3</sub>OH}<sub>n</sub> (1) and {[Mn<sup>II</sup><sub>2</sub>(NITImMe<sub>2</sub>)<sub>3</sub>]ClO<sub>4</sub}<sub>n</sub> (2) where NITImH and NITImHMe<sub>2</sub> are respectively 2-(2-imidazolyl)- (Figure 1a) and 2-(4,5-dimethylimidazol-2-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-3-oxide-1-oxyl (Figure 1b). The molecular replacement technique was used with the [Mn<sup>II</sup><sub>2</sub>(NITIm)<sub>3</sub>] moiety as a search model to phase the crystallographic data and provided a structure with nearly atomic resolution. This major result allows us to first validate the chemical synthesis even from nanocrystals then to establish magnetostructural relationships for these two compounds exhibiting both a long-range 3D ordering of weak-ferromagnetic associated with spin canting and a field-induced metamagnetic transition.
## Results and discussion

**Synthesis and crystal growth:** Compounds {[Mn<sup>II</sup><sub>2</sub>(NITIm)<sub>3</sub>]CF<sub>3</sub>SO<sub>3</sub>·CH<sub>3</sub>OH}n (1) and {[Mn<sup>II</sup><sub>2</sub>(NITImMe<sub>2</sub>)<sub>3</sub>]ClO<sub>4</sub>}n (2) were synthesized following the procedure described previously to yield either VT compounds {[Mn<sup>II</sup><sub>2</sub>(NITIm)<sub>3</sub>]X}n with X= ClO<sub>4</sub><sup>-</sup> (4); BF<sub>4</sub><sup>-</sup> (5), PF<sub>6</sub><sup>-</sup> (6) or compounds exhibiting long range magnetic ordering {[Mn<sup>II</sup><sub>2</sub>(NITBzIm)<sub>3</sub>]ClO<sub>4</sub>}n (3) with NITBzImH (Figure 1c).<sup>16-18</sup> To this end, nitronyl nitroxide radicals (NITImH or NITImHMe<sub>2</sub>) were first mixed with manganese(II) acetate in a 3:2 ratio in methanol, where manganese(II) acetate acts both to provide metal ions and to deprotonate the imidazole moiety. Then compounds were slowly precipitated as polycrystalline powders upon addition of sodium triflate (NaOTf) for 1 or sodium perchlorate (NaClO<sub>4</sub>) for 2. Laboring efforts to grow single crystals of {[Mn<sup>II</sup><sub>2</sub>(NITIm)<sub>3</sub>]OTf}n (1) and {[Mn<sup>II</sup><sub>2</sub>(NITImMe<sub>2</sub>)<sub>3</sub>]ClO<sub>4</sub>}n (2) large enough for X-ray diffraction studies have been unsuccessful. Methanol diffusion into a water solution of the reactants, which allowed crystal growth for previously studied compounds 4-6, was not effective for complexes 1 and 2. Furthermore, although nitronyl nitroxide radicals are quite stable in standard conditions, they should be handle with care, which limits the scope of crystallization techniques to be used. For example, solvothermal synthesis which are common for MOFs cannot be used.

**3D ED data collection:** We used 3D electron diffraction for the structure determination from nano-sized crystalline samples. Diffraction data were collected under low-dose conditions on a Tecnai F20 TEM (Transmission Electron Microscope) operated at 200 kV equipped with a Medipix3RX hybrid pixel detector (Amsterdam Scientific Instruments) as described in the Supplementary Information Section 3. Preliminary beam damage assessment showed that crystallinity loss became visible already at 1.0 e/Å<sup>2</sup>. Thus, pre-exposure was significantly reduced by searching the crystalline particles digitally on low magnification TEM images, and by centering the crystals
(eucentric height tuning) at very low dose with the help of the Medipix3RX detector. The total accumulated dose during data acquisition on the crystals of compound **1** was 4.0 e·Å⁻² (crystal **1**), 3.4 e·Å⁻² (crystal **2**), and 3.8 e·Å⁻² (crystal **3**), while the compound **2** crystal was irradiated with 3.1 e·Å⁻².

**Crystal structures:** Compound **1** crystallizes in monoclinic space group *P*2₁ and compound **2** in the orthorhombic space group *P*2₁2₁2₁ (Table S1-S2). Interestingly, crystal structures of previously described 2D manganese-radical frameworks were also found to crystallize in these non-centrosymmetric space groups (Table S3).¹⁶, ¹⁷, ¹⁹, ²⁰ The resolution, less than 1.2 Å for most data, was not high enough for *ab initio* structure solution.⁴³,⁴⁴ The crystal structure was then solved by the molecular replacement method using the structural motif [MnII₂(NITIm)₃] from the crystal structure of {[MnII₂(NITIm)₃]ClO₄}n (4) at 300 K (CSD entry # 100351) as a search model. This allowed the structure determination of both compounds (Figure 2) and their refinement against 3D ED data, using the kinematical approximation. The detailed description of the structure solution and refinement is provided in the Supplementary Information. The X-ray powder diffraction patterns and the simulated one from the refined structures are in good agreement for compound **2** (Figure S2) while for compound **1** there is agreement for the positions of the Bragg pics but discrepancy for their intensities (Figure S1). This is attributed to the preferential orientation of the nanocrystals, which are platelet-shaped. For compound **2** the structure of the perchlorate anion was also taken from the crystal structure of **4** at 300 K, while for compound **1** the structure of the triflate anion was taken from a published crystal structure elsewhere.⁴⁵ Both anions could be placed unambiguously in the residual {Fobs - Fcalc} Coulomb potential map.

Inorganic Chemistry Frontiers Accepted Manuscript
<figure><img src="image_5.png" /><figcaption>**Figure 2.** View of the 2D metal-radical frameworks: a) {[Mn<sup>II</sup><sub>2</sub>(NITIm)<sub>3</sub>]OTf}n (1) and b) {[Mn<sup>II</sup><sub>2</sub>(NITImMe<sub>2</sub>)]ClO<sub>4</sub>}n (2) along the *c* axis direction layered with c) OTf (1) and d) ClO<sub>4</sub><sup>-</sup> (2) anions viewed along the *a* axis direction. Mn<sup>2+</sup> ions are depicted in pink with coordination polyhedra (a and b). Atoms are depicted as follows: Mn, pink; O, red; N, dark blue, S, yellow, F, light blue and Cl, green; H atoms and CH<sub>3</sub>OH solvent molecules are omitted for clarity.</figcaption></figure>
<figure><img src="image_6.png" /><figcaption>**Figure 3.** a) View of one cation moiety $[Mn^{II}_2(NITIm)_3]^+$ in compound 1 showing manganese ions Mn1 and Mn2 with respectively *fac*-Δ and *mer*-Δ alternating conformations. Symmetry related atoms: i: (-1+x, y, z); ii: (-x, -0.5+y, -z); iii: (-x, 0.5+y, -z); iv: (1+x, y, z). b) View of the cation moiety $[Mn^{II}_2(NITImMe_2)_3]^+$ in compound 2 showing manganese ions Mn1 and Mn2 with Δ and Λ alternating conformation but both with *mer* arrangement of the ligands. Symmetry-related atoms: ix: (-1-x, -0.5+y, -0.5-z); x: (-x, -0.5+y, -0.5-z); xi: (-1-x, 0.5+y, -0.5-z); xii: (-x, 0.5+y, -0.5-z). Atoms are depicted as follows: Mn, pink; O, red; N, blue; H atoms are omitted for clarity.</figcaption></figure>
Compounds **1** and **2** crystallize as layered structures. The sheets are made of 2D positively charged coordination polymers {[Mn<sup>II</sup><sub>2</sub>(NITIm)<sub>3</sub>]<sup>+</sup>}<sub>n</sub> (**1**) and {[Mn<sup>II</sup><sub>2</sub>(NITImMe<sub>2</sub>)<sub>3</sub>]<sup>+</sup>}<sub>n</sub> (**2**) with honeycomb-like structures growing along the **ab** plane direction (Figure 2a and 2b). These sheets are separated along the **c** axis by layers of OTf<sup>-</sup> (**1**) or ClO<sub>4</sub><sup>-</sup> (**2**) counter-anions layers (Figure 2c and 2d). CH<sub>3</sub>OH solvent molecules were found together with triflate anions in inter-sheets space in compound **1** while compound **2** crystallizes as a solvent-free layered structure.

In structure of **1** there are two crystallographically independent {[Mn<sup>II</sup><sub>2</sub>(NITIm)<sub>3</sub>]OTf·CH<sub>3</sub>OH} moieties in the asymmetric unit, leading to four Mn(II) centers denoted Mn1, Mn2, Mn3 and Mn4 (Figure 3a, Figure S3). For compound **2**, only one {[Mn<sup>II</sup><sub>2</sub>(NITImMe<sub>2</sub>)<sub>3</sub>]ClO<sub>4</sub>}<sub>n</sub> moiety is found in the asymmetric unit with two crystallographically independent Mn(II) centers denoted Mn1 and Mn2 (Figure 3b). As for any coordination polymers built on metal centers with three coordinated *bis*-chelating ligands, the 2D honeycomb-like structure is made of the alternation of Λ and Δ coordination stereoisomers. Here the Λ conformation for Mn1 (**1** and **2**) and Mn4 (**1**), and Δ conformation for Mn2 (**1** and **2**) and Mn3 (**1**) (Figure 3 and S3). For compound **2**, the radicals coordinated to the Mn1 and Mn2 metallic centers are in the *mer* conformation, as observed in other analogous compounds **3-6**.<sup>17-19</sup> Interestingly for compound **1**, the radicals coordinated to the Mn1 and Mn3 centers are in the *mer* arrangement while the ones bound to Mn2 and Mn4 are in the *fac* conformation. Among compounds with 2D Mn-radical frameworks, compound **1** is the first to show the *fac* arrangement of the radical. The *fac* arrangement was also found in the isolated complex [Mn<sup>II</sup>(NITIm)<sub>3</sub>](ClO<sub>4</sub>)<sub>2</sub>.<sup>46</sup>

In compound **1**, the {[Mn<sup>II</sup><sub>2</sub>(NITIm)<sub>3</sub>]}<sub>n</sub> sheets are highly corrugated along the **b** direction (Figure 2c and Figure S4). The Mn2 and Mn4 are ±1.43 Å apart from the mean plane containing the Mn1 or Mn3 (Figure S5). Moreover, and quite remarkably, the successive corrugated sheets

Inorganic Chemistry Frontiers Accepted Manuscript
are not stacked in the classical manner of crest on crest (trough on trough), but are staggered in an almost crest on trough stacking. This appears to be due to intermolecular bonding involving the -CF₃ and -SO₃⁻ moieties of the triflate anions, which brings the crests of the lower 2D-sheets closer to the troughs of the upper ones (Figure 2c). This yields empty channels running along the *a* axis direction (Figure S6). This is in contrast to the nearly flat {[Mn¹¹₂(NITImMe₂)₃]}ₙ 2D sheets in compound **2** (Figure 2d and Figure S7), where Mn1 and Mn2 just slightly deviate (±0.36Å) from their mean plane (Figure S8), reminiscent of what was observed in the structure of analogous compounds **3-6**.¹⁷⁻²⁰

In both compounds, each Mn is hexacoordinated by three O atoms and three N atoms from three chelated nitronyl nitroxide radicals with the Mn-O and Mn-N bond lengths falling in the 1.98–2.3 Å range for compound **1** (Table S4-S5) and in the 2.00–2.32 Å range for compound **2** (Table S6-S7). These bond lengths are typical for Mn(II) coordination with N- and O-based ligands, particularly with Mn-nitroxide compounds.⁴⁶

The structural features within the metal-radical frameworks are constrained by the chelation of the Mn²⁺ ions to the radicals with slight variations within the family of different coordination polymers depending on the type of nitronyl nitroxide radicals. Thus, in 1D systems {[Mn¹¹(NITIm)}ₙ built from NITImH radical, the Mn---Mn distances between the first neighbors and the second neighbors were found to be 6.33–6.40 Å and 9.59–9.94 Å respectively within the infinite chain.⁴⁶ Similar Mn---Mn distances were also found for 2D compound **4** above 300 K (6.21–6.28 Å and 9.88–11.30 Å respectively).¹²ᵃ These structural parameters are also observed within the plane in compounds **1** and **2**. The Mn---Mn first and second neighbor distances are respectively in the ranges 6.31–6.40 Å and 9.83–11.81 Å for **1** and 6.46–6.48 Å and 10.32–11.95 Å for **2** (Table S3 and S5). In compounds **1** and **2** the Mn centers build a hexagonal network where

Inorganic Chemistry Frontiers Accepted Manuscript
the hexagons are either aligned but slightly elongated along the **b** axis (1) (Figure S5) or tilted and forming zigzag along the **b** direction (2) (Figure S8). Although the unit cell of compound 1 and 2 contains the same number of [Mn<sup>II</sup><sub>2</sub>(NITIm)<sub>3</sub>] or {[Mn<sup>II</sup><sub>2</sub>(NITImMe<sub>2</sub>)<sub>3</sub>], the **a** parameter and cell volume of compound 1 are larger than those of compound 2, as shown in Table S2. This suggests that OTf<sup>-</sup> anion requires more space than ClO<sub>4</sub><sup>-</sup> anion and the six Me-substitutions per formula unit for complex 2. This may be also the reason why compound 1 show alternation of the *mer* and *fac* arrangements of the radicals.

Relevant structural features to consider for magneto-structural relationships is the dihedral angle α between the plane (P2) going through atoms of the nitronyl nitroxide moiety (O-N-C-N-O) and the plane (P1) going through the coordination atoms (O-Mn-N) as shown on Figure S9. Indeed, the unpaired electron of nitronyl nitroxide is located in the π* orbital which is perpendicular to the P2 plane going through atoms O-N-C-N-O. Therefore, as the dihedral angle α decreases, this increases the overlap of the π* and *d* magnetic orbitals and, as a result, the magnetic interaction between the radical and Mn(II) is expected to become more antiferromagnetic (Figure S9).<sup>47</sup> In compound 1 (Table S9) the α dihedral angles are in the range 12.37-46.12° for Mn1-Mn2 and in the range 16.80-35.75° for Mn3 and Mn4. In compound 2 they are in the range (4.54-38.56°). It is also important to examine the dihedral angle or torsion angle φ between the P2 plane and the (P3) plane passing through the N-C-N atoms of the imidazole substituent to assess the deviation from coplanarity of the nitronyl nitroxide radical. In compound 1 the dihedral angles φ (Figure S9) are in the range 10.23-24.15° for Mn1-Mn2 (Table S8a) and in the range 10.45-19.06° for Mn3 and Mn4 (Table S8b) while for compound 2 it is in the range 7.18-14.27° (Table S10). These values are relatively small compared with 48.4° found for the nitronyl nitroxyde alone and may be ascribe to the constraint effect of coordination.

Inorganic Chemistry Frontiers Accepted Manuscript
Magnetic studies:

<figure><img src="image_7.png" /><figcaption>**Figure 4:** χT (left, plain square) and 1/χ (right, open squares) vs T for {[Mn₂(NITIm)₃]OTf·CH₃OH}n (1) at magnetic field H = 1 kOe. The blue (χT) and red (1/χ) solid lines represent the fit of the data with a mixed quantum-classical Heisenberg model as described in the text.⁴⁸</figcaption></figure>
Magnetic measurements were carried out on bulk crystalline powders, whose X-ray diffraction patterns were checked for agreement with those calculated from electron diffraction crystal structures, as described in the section on crystal structures (Figures S1-S2). {[Mn₂(NITIm)₃]OTf·CH₃OH}n (1) and {[Mn₂(NITImMe₂)₃]ClO₄}n (2) exhibit similar magnetic behavior. At 300 K under a magnetic field of 1 kOe, the χT product is 7.45 cm³·K·mol⁻¹ (1) (Figure 4) and 7.65 cm³·K·mol⁻¹ (2) (Figure S10). These values are well below what would be expected (9.875 cm³·K·mol⁻¹) for the uncorrelated spins comprising two Mn²⁺ (S = 5/2) and three radicals (S = 1/2). For both compounds, upon cooling, χT increases continuously to reach a maximum value around 40 K, a value that is magnetic field-dependent. The inverse of the magnetic susceptibility (1/χ) versus temperature are linear in the temperature range 150–300 K (Figure 4 (1) and Figure S10 (2)), following a Curie-Weiss behavior with θ values of 83 K (1) and 87 K (2) and Curie constant C = 5.37 cm³ K mol⁻¹ (1) and C = 5.40 cm³ K mol⁻¹ (2). These behaviors are similar to those shown by {[Mn₂(NITBzIm)₃]ClO₄}n (3).¹⁸ This is due to alternating spins S = 5/2 and S = 1/2 which are antiferromagnetically coupled within the 2D metal-radical frameworks. In the temperature range studied, the 2D networks behave like ferromagnetically coupled Sₜot = 7/2 effective units resulting from two Mn²⁺ ions antiferromagnetically coupled with three radicals. The magnetic susceptibility was fitted using the mixed quantum-classical Heisenberg model reported for a 2D honeycomb structure with alternating Mn²⁺ and Cu²⁺ ions.⁴⁸ A good agreement with experimental data was obtained for both compounds 1 and 2 in the temperature range 300–150 K, (Figure 4 and Figure S10), which is well within the limit of the given reliability of the model. The best fit gives an antiferromagnetic interaction J = -44.2(4) cm⁻¹ (H = -2JΣSᵢSⱼ) (with gᵣad = 2.00(2) and gMn=2.08(2) between the Mn²⁺ ion and the radical of compound 1 (Figure 4) and J = -44.9(5) cm⁻¹ (H = -2JSᵢSⱼ) with gᵣad = 2.00(2) and gMn=2.00(2) between the Mn²⁺ ion and the radical of
compound 2 (Figure S10). Below 150 K the model is unable to fit the experimental data (Figure 4) as it does not take into account the three-dimensional magnetic ordering. The goodness of fit value is further supported by these *J* values, which are of the same order of magnitude as those found in the mononuclear complex [Mn(NITImH)₃](ClO₄)₂ (*J* = -53(2) cm⁻¹)⁴⁶ and in 1D compounds with bridging NITIm⁻ nitroxide radicals (-43(3) < *J*< -86(5) cm⁻¹).⁴⁹ For such a ferrimagnetic behavior, a minimum of χT is expected at 365 K, but this temperature is above the thermal stability limit for both compounds.⁴⁸

<figure><img src="image_8.png" /><figcaption>**Figure 5:** Field dependence of the magnetization for **1** (square) and **2** (circle) at 2 K (1st magnetization). The insert zooms in on the behavior in the low magnetic field range (0–700 Oe).</figcaption></figure>

For both compounds, the first magnetization curves are sigmoidal. They show two magnetic regions, which are reminiscent of a metamagnetic transition.⁵⁰ At low magnetic fields (region I),
the magnetization increases almost linearly (insert Figure 5 and Figure S11) up to a bend at 225 Oe for **1** and at 100 Oe for **2**, as determined by a zero of the second derivative. Beyond these respective values (region II), the magnetization increases asymptotically to reach 6.58 µB and 6.23 µB at 15 kOe for compounds **1** and **2**, respectively (Figure 5). Further then, they continue to increase slowly, reaching 6.72 µB (**1**) and 6.41 µB (**2**) at 50 kOe, but do not reach the expected M = 7 µB saturation value for an effective S<sub>tot</sub> = 7/2. Similar magnetic behavior was also found for other 2D and 1D coordination polymer-based compounds based on Mn<sup>2+</sup> ions and nitronyl nitroxide radicals and it was ascribed to spin-canting within the 2D layers.<sup>18, 49, 51-53</sup>

<figure><img src="image_9.png" /><figcaption>**Figure 6:** Zero field cool (red triangles) and field cool (blue triangles) magnetization for **1** in a magnetic field of H = 500 Oe. The insert shows the derivative (dT/dM) in the T<sub>c</sub> region.</figcaption></figure>
Zero field cool (ZFC) and field cool (FC) measurements and AC measurements confirm the existence of the two magnetic regions evidenced by first magnetization curves (insert Figure 5 and Figure S11). For compound **1** the ZFC/FC curves shows the onset of bifurcation only for magnetic field above 500 Oe, that is beyond the linear region I of the first magnetization, with a divergence of 3.5μB at 2K (Figure 6). For compound **2** bifurcation between the ZFC/FC curves is already observed from 100 Oe with a divergence of 2μB at 2K (Figure S16). The first derivative on FC provides Curie temperatures T_c = 45 K for **1** (Figure 6) and T_c = 40 K for **2** (Figure S16), which are lower than those found for compound **3** (T_c = 55 K).¹⁸ It is comparable to the Curie temperature (T_c = 46 K) found for assemblies of Mn²⁺ ions and trinitroxide radicals with a quartet ground state.⁵⁴

<figure><img src="image_10.png" /><figcaption>**Figure 7:** Temperature dependence of the real part χ' and imaginary part χ'' of the susceptibility at AC field frequencies 10 (black), 100 (green), 500 (red), and 1400 (blue) Hz and 0 Oe applied dc for compound **1**.</figcaption></figure>
The AC susceptibility data are shown in Figure 7 (1) and Figure S17 (2). There are frequency-independent peaks at 43 K for 1 and 39 K for 2 both in the real part (χ') and imaginary part (χ") which are the signature of the onset of three-dimensional long-range ferromagnetic ordering and are in good agreement with Curie temperature found from ZFC/FC measurements. The bulges in the real part (χ') and peaks in imaginary part (χ") visible for 1 at lower temperatures which are little frequency-dependent, are ascribed to slow relaxation of magnetization within the 2D layers.

<figure><img src="image_11.png" /><figcaption>**Figure 8:** Field dependence of the magnetization upon cycling for 1 (square) at 2 K. The inset zooms in on the hysteresis loop.</figcaption></figure>

Three-dimensional ferromagnetic ordering is confirmed by cycling the field-dependence of the magnetization for both compounds 1 and 2 which exhibit a butterfly-shaped hysteresis that tightens
but does not vanishes at zero magnetic field and gives a small but coercive field of 50 Oe at 2 K (Figure 8 and Figure 9). Reports of metamagnets exhibiting coercive field is not unusual<sup>55-60</sup> despite it is not expected as the hysteresis should be confined above the field induce transition.<sup>61</sup>

The explanation for such a coercive but weak field in our case is that once the spins have flipped into the ferromagnetic phase, this induces an increase in magnetic anisotropy, so that their reversal to the antiferromagnetic phase requires more energy. In other words, the sweep rate used in the measurements (0.5 Oe/s) may be faster than the relaxation time, so the spins may not follow. This results in the constriction around the zero field without canceling out.<sup>55, 62-64</sup> This may depend on chemical factors, but also on the size and shape of the grains in the compounds.

<figure><img src="image_12.png" /></figure>

<figure><img src="image_13.png" /></figure>
**Figure 9:** Hysteresis loop zoom (-600 – 600 Oe) for **1** (a, square) and for **2** (b, circle) with first magnetization for **1** (a, filled square) and for **2** (b, filled circle) at scan rate 0.5 Oe/s.

The hysteresis loops close up at 4 µB for both compounds **1** and **2** (Figure 8), far from the magnetization maximum values of 6.72 µB (**1**) and 6.41 µB (**2**) reached at 50 kOe (Figure 5), and this argues for spin-canting within the 2D metal-radical framework sheets. In addition, the hysteresis loops for both compounds deviate from the initial magnetization curves. This behavior, together with the temperature dependence of the ZFC magnetic susceptibilities (Figures S12-S16) at different magnetic fields, which supports two different magnetic phases, also argues in favor of a metamagnetic transition. The 2D spin-canted metal-radical framework sheets {[Mn<sup>II</sup><sub>2</sub>(NITIm)<sub>3</sub>]<sup>+</sup>}<sub>n</sub> (**1**) and {[Mn<sup>II</sup><sub>2</sub>(NITImMe<sub>2</sub>)<sub>3</sub>]<sup>+</sup>}<sub>n</sub> (**2**), which are antiferromagnetically coupled below 500 Oe for **1** and 100 Oe for **2**, undergo a magnetic field-induced transition to ferromagnetic coupling at higher fields, with the onset of long-range weak ferromagnetic ordering.

Metamagnetic transitions in molecule-based magnets have been reported elsewhere,<sup>63, 65-70 58, 71-73</sup> including several cases with spin-canting coexistence.<sup>58, 71-73</sup> Similar behavior was supported by neutron diffraction studies of previously reported enantiopure 1D-chain molecular ferromagnets.<sup>51-53</sup> From the neutron study, the magnetic structure of this compound can be described as stacked canted ferromagnetic sheets that are antiferromagnetically coupled in zero field, but ferromagnetically coupled when a magnetic field is applied.<sup>52, 53</sup> This was ascribed as due to long-ranged but weak antiferromagnetic dipolar coupling prevailing between the layers with canted spin at low magnetic field while a ferromagnetic coupling between the layers is prevails at high fields.

The same magnetic field-induced reversal between antiferromagnetic and ferromagnetic long-range ordering near T<sub>c</sub> should occur in compounds **1** and **2**. The origin of magnetic anisotropy associated with spin canting is still questionable owing Mn<sup>2+</sup> ions and nitronyl nitroxide radicals

Inorganic Chemistry Frontiers Accepted Manuscript
are not expected to have anisotropy. As in reported Mn-radical chain compounds the dipolar interaction is hold as the main source of the magnetic anisotropy in these layered compounds.⁴⁷, ⁴⁹, ⁵³, ⁷⁴, ⁷⁵ Moreover, the Dzyaloshinskii-Moriya (DMI) antisymmetric exchange interaction may be at the origin of the canted spin as this compound crystallizes in non-centrosymmetric space groups (P21 and P212121).⁷⁶, ⁷⁷

The fact that compounds **1** and **2**, as well as **3**, do not exhibit VT behavior like compounds **4-6** supports our hypothesis that the distance between the 2D metal-radical framework layers is a key parameter for inducing the intra-sheet electron-charge transfer. In the previously reported compounds with the NITIm⁻ radical (**4-6**), the largest interlayer distance was 10.85 Å at room temperature for compound **6** with the PF₆⁻ anion, which was the largest anion in the series. For compounds **1-3**, this interlayer distance at room temperature (Table S3) is larger by 0.5 Å for **2** and by more than 1.5 Å for **1** and **3**. Moreover, compound **6** was stabilized in the Mn¹¹¹ redox tautomeric form at room temperature [Mn¹¹¹₂(NITIm)(NITRed)₂]PF₆]n.¹⁹ This suggests that the PF₆⁻ anion may induce a higher chemical pressure than the ClO₄⁻ and BF₄⁻ anions, favoring the stabilization of the redox tautomeric phase characterized by a smaller volume.⁷⁸ In contrast, compounds **1-3** are stabilized in the Mn¹¹¹ tautomeric form {[Mn¹¹¹₂(radical)₃]X}n (radical: NITIm⁻ (**1**), NITImMe₂⁻ (**2**), NITBzIm⁻ (**3**); X= ClO₄⁻ (**2, 3**) or OTf⁻ (**1**)) and over the whole temperature range (2–300 K). We can see that the densities of compounds **1-3** are lower than those of **4-6** (Table S3), indicating a decrease in solid state compactness, which may induce less chemical pressure favoring the high-spin tautomer for compounds **1-3**. This agrees with the stabilization of the Mn¹¹¹ redox tautomer at higher temperature when a mild external pressure is applied on compounds **4-6**.²⁰

As with spin crossover and other phenomena involving electron transfer, features of valence tautomeric conversion such as abruptness and hysteresis depend on cooperativity and flexibility.⁷⁹-
⁸¹ Cooperativity is attributed to weak intermolecular interactions and electrostatic contributions

Inorganic Chemistry Frontiers Accepted Manuscript
and is expected to decrease with increasing interlayer distance in our 2D frameworks.⁸², ⁸³ The flexibility of the molecular system can be seen as its ability to “breathe”. That is being capable of structure transformation upon electron relocation as this involves many small changes in bond lengths and bond angles.⁷⁹⁻⁸¹

The fact that compounds **1** and **2**, as well as **3**, do not exhibit VT may be due to a lower flexibility of their 2D metal-radical layers. For **2** and **3**, because of the higher steric hindrance of the dimethyl (NITImMe₂⁻) and benzimidazole (NITBzIm⁻) substituents compared to the NITIm⁻ radical. For compound **1**, the triflate anions bind the layers more strongly through intermolecular bonds involving the -CF₃ and -SO₃⁻ moieties. Thus, it appears that in compounds **1-3**, greater separation in-between the 2D metal-radical layers, lower densities and enhanced rigidity combine to stabilize the compounds as {[MnII₂(radical)₃]X}n.

## Conclusion

We have succeeded in synthetizing two new complexes, {[MnII₂(NITIm)₃]OTf·CH₃OH}n (1) and {[MnII₂(NITImMe₂)₃]ClO₄}n (2) crystallizing as layered compounds made of 2D metal-radical frameworks {[MnII₂(radical)₃]⁺}n with interleaved layers of anions (X) for electro-neutrality and succeed to unveil the crystal structure by using 3D ED. The result is all the more remarkable in that these two compounds produce only nano-sized crystalline powders, which could never be grown to a crystal size allowing X-ray diffraction characterization of a single crystal, and are furthermore electron-sensitive due to their organic radical nitronyl nitroxide components.

The magnetic characterization shows that the two compounds exhibit a ferrimagnetic behavior within the 2D metal-radical frameworks due to an alternation of antiferromagnetically coupled spins (S<sub>Mn</sub><sup>2+</sup> = 5/2 and S<sub>radical</sub> = 1/2). Furthermore, they highlight a field-induced metamagnetic
transition from antiferromagnetic coupling (region I) to predominantly ferromagnetic coupling (region II) associated with change of spin-canting angle between the 2D metal-radical layers. Both compounds undergo a long-range 3D weak ferromagnetic ordering in region II with the Curie temperature $T_c = 45$ K (1) and 40 K (2). This behavior differs from that of the analogous compounds **4-6**, which have a similar layered structure, but different anions or substituents on the radical, and exhibit valence tautomerism. Comparative crystal structure analysis highlights the complex interplay between factors such as interlayer distance, anion size, chemical pressure, and framework flexibility to stabilize compounds **1** and **2** as the {[Mn<sup>II</sup><sub>2</sub>(radical)<sub>3</sub>]X<sub>n</sub>} tautomers.

Moreover, this work illustrates, how crucial it is to obtain crystal structures, and how electron crystallography can be used to cross the crystal size barrier and to elucidate complex structures even with beam-sensitive nanoscale crystals. Even when the resolution does not match the criteria for solving the structure by *ab initio* methods, other phasing methods such as molecular replacement can be successfully used. Herein we show that by providing a nearly atomic resolution on nanocrystals of compounds **1** and **2**, 3D ED was the key to ultimately allowing us to establish magneto-structural correlations for these two compounds. Recent methodological progress in electron diffraction should provide further breakthroughs in the field of molecule-based magnets and other area related to coordination polymers in which conventional X-ray diffraction techniques cannot be used to provide accurate 3D structural information. For our part, we can now envisage systematic studies with metals other than manganese, and tackling the design of 3D compounds based on the same metal-radical approach where crystal structure characterization is essential to ensure we get the right architecture and develop advanced materials.

## Experimental
All experimental details on synthesis and characterization including powder XRD patterns and additional Tables and Figures for crystal structures and magnetism are in the ESI supported by additional references.¹⁶⁻²⁰, ⁸⁴⁻⁸⁸

**Data availability**

The datasets supporting this article have been uploaded as part of the ESI.

**Author contributions**

E. Yörük., D. Housset., W. L. Ling, S. Kodjikian and H. Klein: ED studies; C. Lecourt, Y. Izumi, C. Desroches, K. Inoue, E. Tretyakov, K. Maryunina: synthesis and magnetic studies. D. Luneau: project conception, discussion and supervision.

**Conflicts of interest**

There are no conflicts to declare.
**Supplementary Information**

Electronic supplementary information (ESI) available: CCDC 2330279 (1) and 2330280 (2)

For ESI and crystallographic data in CIF or other electronic format see DOI:

**Acknowledgement**

**Dedication:** The authors dedicate this paper to the memory of Victor Ovcharenko for his seminal work in the field of molecular magnetism and the metal-radical approach.

We thank Dr. Guy Schoehn for setting up and maintaining the IBS/ISBG EM platform and for discussion and Emmanuelle Neumann for training on the F20 cryo-electron microscope. IBS acknowledges integration into the Interdisciplinary Research Institute of Grenoble (IRIG, CEA). We acknowledge the support of JSPS Summer Program 2017 for an internship fellowship in Hiroshima University to C. L. We thank the Faculté des Sciences at Université Claude Bernard Lyon 1 for internship support to Y. I. This work was supported by CNRS collaborative research program (PRC 2017-2019 No. 1536), by the Russian Science Foundation (grant No. 21-73-20079) and Magdesign Project (ANR-22-CE29-0018-03). Platforms of the Grenoble Instruct-ERIC center (ISBG; UAR 3518 CNRS-CEA-UGA-EMBL) within the Grenoble Partnership for Structural Biology (PSB), supported by FRISBI (ANR-10-INBS-0005-02) and GRAL, financed within the University Grenoble Alpes graduate school (Ecoles Universitaires de Recherche) CBH-EUR-GS (ANR-17-EURE-0003). The IBS-ISBG electron microscope facility is supported by the Région Auvergne-Rhône-Alpes, Fondation pour la Recherche Médicale (FRM), Fonds FEDER and the GIS-Infrastructures en Biologie Santé et Agronomie (IBiSA). This work was also supported by Grant-in-Aid for Scientific Research (Nos. 25220803, 22H02053), CResCent (Chirality Research
Center) in Hiroshima University (the MEXT program for promoting the enhancement of research universities, Japan) and Core-to-Core Program, A. Advanced Research Networks.

**Keywords**

Electron diffraction; metal-radical coordination frameworks; manganese(II); nitronyl nitroxide radicals; molecular magnets

**Notes and References**

**Present addresses:** C. Lecourt: Institut Parisien de Chimie Moléculaire (UMR 8232), Sorbonne Université, 75252 Paris cedex 05, France; E. Yörük: Department of Structure Analysis, Institute of Physics of the Czech Academy of Sciences, Cukrovarnická 10, 162 00 Prague 6, Czechia; K. Maryunina: International Tomography Center SB RAS, 3A Institutskaya Street, Novosibirsk 630090, Russian Federation and Novosibirsk State University, Pirogova Str., 2, Novosibirsk 630090, Russian Federation

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Data availability

The datasets supporting this article have been uploaded as part of the ESI.

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DOI: 10.1039/D4QI02257B

Inorganic Chemistry Frontiers Accepted Manuscript