Synthesis, Structural, Magnetic and Computational Studies of a One-Dimensional Ferromagnetic Cu(II) Chain Assembled from a New Schiff Base Ligand

Abstract

A new asymmetrically substituted ONOO Schiff base ligand N-(2′-hydroxy-1′-naphthylidene)-3-amino-2-naphthoic acid (nancH₂) was prepared from the condensation of 2–hydroxy–1–naphthaldehyde and 3–amino–2–naphthoic acid. nancH₂ reacts with Cu₂(O₂CMe)₄·2H₂O in the presence of Gd(O₂CMe)₃·6H₂O to afford a uniform one-dimensional homometallic chain, [Cu^II(nanc)]_n (1). The structure of 1 was elucidated via single crystal X-ray diffraction studies, which revealed that the Cu(II) ions adopt distorted square planar geometries and are coordinated in a tridentate manner by an [ONO] donor set from one nanc²⁻ ligand and an O⁻ of a bridging carboxylate group from a second ligand. The bridging carboxylato group of the nanc²⁻ ligand adopts a syn, anti-η¹:η¹:μ conformation linking neighboring Cu(II) ions, forming a 1D chain. The magnetic susceptibility of 1 follows Curie–Weiss law in the range 45–300 K (C = 0.474(1) emu K mol-1, θ = +7.9(3) K), consistent with ferromagnetic interactions between S = ½ Cu(II) ions with g = 2.248. Subsequently, the data fit well to the 1D quantum Heisenberg ferromagnetic (QHFM) chain model with g = 2.271, and J = +12.3 K. DFT calculations, implementing the broken symmetry approach, were also carried out on a model dimeric unit extracted from the polymeric chain structure. The calculated exchange coupling via the carboxylate bridge (J = +13.8 K) is consistent with the observed ferromagnetic exchange between neighbouring Cu(II) centres.

1. Introduction

Coordination polymers have garnered significant interest due to their potential for displaying fascinating magnetic behaviour [1,2,3,4,5,6,7,8], and have found applications in various fields, including catalysis [9] and medicinal chemistry [10], among others [11,12,13]. There has been considerable attention paid towards low-dimensional materials which can exhibit unusual forms of magnetic response, depending on the dimensionality of the exchange pathway and the type of spin system. These can lead to examples of spin frustration [14,15], Koesterlitz–Thouless transitions in two-dimensional systems [16,17], and the emergence of Haldane gaps in one-dimensional chains [18,19]. One-dimensional materials comprise examples of both regular chains (a single exchange term), or alternating chains (comprising two magnetic exchange terms which may be ferromagnetic, antiferromagnetic, or a mixture of both ferro- and antiferromagnetic) [20,21]. When Ising-like spins are involved, such systems can lead to ‘single chain magnets’ in which there is a gapped state with slow relaxation [22,23]. Some of the most well-studied low-dimensional models comprise one-dimensional (1D) Heisenberg S = ½ magnetic compounds [24,25,26]. In this respect, the magnetic insulator copper pyrazine dinitrate has provided a unique opportunity for a quantitative comparison between theory and experiment [26]. For such isotropic spins, a unique expression for their susceptibility is not possible, but expressions in the case of both antiferromagnetic and ferromagnetic exchange have been put forward. In the case of ferromagnetic exchange, such regular 1D chains can be well-described by the 1D quantum Heisenberg ferromagnet (1D QHFM) equation (Equation (1)), defined by the Hamiltonian in Equation (2) [27,28,29]. The values of the numerator (N_i) and denominator (D_i) in Equation (1) are tabulated elsewhere [30]. Cu(II)-based polymers provide good models for exploring such behaviour [31,32,33], and comprise one of the most well-studied 1D systems to date [26,34,35,36,37].

(1)${\mathsf{\chi }}_{mol}\left(1-D QHFM\right)=\frac{C_{mol}}{T}\left[\frac{1+{\sum }_{i=1}^3{N}_i{\left(\frac{J}{k_{B}T}\right)}^i}{1+{\sum }_{i=1}^4{D}_i{\left(\frac{J}{k_{B}T}\right)}^i}\right]$

(2)$H=-J{S}_i·S_j$

Molecular self-assembly of 3d metal ion complexes with polydentate ligands has been shown to be an effective method of generating coordination polymers [38,39,40,41,42]. Schiff bases are particularly appealing as they have been reported to exhibit valuable properties, lending themselves to the formation of compounds with a broad range of industrial and biological applications [43,44,45,46,47,48,49,50]. Thus, this class of ligands are attractive and can be readily synthesized from the condensation reaction between an amine and a carbonyl compound. The incorporation of one or more donor atoms into the Schiff base backbone affords polydentate ligands which can stabilize complexes with various transition metals due to the chelate effect [51,52,53,54,55,56,57]. Moreover, including hydroxy or carboxylate functional groups provides bridging ligands to construct coordination clusters or polymers and has proven to be an effective approach [58,59,60,61], exemplified by Schiff bases with a naphthalene-based organic scaffold which have been successfully used to isolate 1-D magnetic chains [62,63,64,65]. In the current study, we utilized the new tetradentate chelating/bridging Schiff base ligand N-(2′-hydroxy-1′-naphthylidene)-3-amino-2-naphthoic acid (nancH₂), (Scheme 1) in Cu(II) coordination chemistry, through utilizing the serendipitous assembly approach. As mentioned previously, these systems provide excellent models for studying fundamental magnetic behaviour in 1D systems that are strongly correlated to the magnetic exchange pathway and the type of spin system. To expand our fundamental understanding of such systems, we report herein the synthesis, magnetostructural, and DFT studies of a new, one-dimensional chain, [Cu^II(nanc)]_n (1).

2. Materials & Methods

General Considerations: All manipulations were performed under aerobic conditions using materials (reagent grade) and solvents as received from Sigma-Aldrich. Elemental analyses were carried out on a PerkinElmer 2400 Combustion CHN Analyser. IR spectra were obtained on solid samples using a Bruker Alpha FT-IR spectrometer, equipped with ALPHA’s Platinum ATR single reflection module. Electrospray ionization (ESI) mass spectra were acquired from a DCM/MeOH solution of nancH₂ by utilizing a Bruker Avance DPX-400 MHz instrument. The NMR spectra were obtained using a Bruker AVANCE III HD 400 MHz in DMSO-d₆ solvent. The NMR spectra are reported relative to tetramethylsilane (ẟ = 0 ppm).

Preparation of N-(2′-hydroxy-1′-naphthylidene)-3-amino-2-naphthoic acid (nancH₂): 2–Hydroxy–1–naphthaldehyde (2.58 g, 15 mmol) and 3–amino–2–naphthoic acid (2.78 g, 15 mmol) were added to methanol (40 mL) and refluxed for 2 h. A yellow powder was isolated by filtration and dried in air. Yield (3.58 g, 70%). Mp 268 °C; ¹H NMR (ppm, DMSO-d₆) 6.86 (d, 1H), 7.32 (t, 1H), 7.51–7.74 (m, 4H), 7.87 (d, 1H), 8.07 (dd, 2H), 8.44 (t, 2H), 8.62 (s, 1H), 9.51 (s, 1H). ¹³C NMR (ppm, DMSO-d₆) 108.9 (CH-C₉H₆CO₂H), 116.4 (CH-C₉H₇O), 120.2 (CH-C₉H₆CO₂H), 122.1 (CH-C₉H₇O), 123.5 (CH-C₉H₆CO₂H), 123.9 (CH-C₉H₆CO₂H), 126.3 (C-C=N), 126.4 (CH-C₉H₇O), 127.4 (C-C₉H₈O), 128.2 (C-C₉H₇CO₂H), 128.8 (C-C₉H₇CO₂H), 129.9 (C-C₉H₈O), 132.4 (CH-C₉H₇O), 133.7 (CH-C₉H₇O), 135.2 (C-OH), 138.0 (C-CO₂H), 139.7 (C-N), 167.4 (C=N), 174.7 (C=O). Mass spectrum (m/z, ESI⁻): 339.9(M-1). IR data (cm⁻¹): 2995, 1702, 1628, 1604, 1588, 1544, 1491, 1459, 1408, 1370, 1346, 1302, 1246, 1214, 1195, 1142, 1043, 974, 925, 866, 840, 786, 747, 732, 689, 655, 628, 584, 566, 555, 525, 503, 470, 423, 408.

Preparation of [Cu^II(nanc)]_n (1): Cu₂(O₂CMe)₄·2H₂O (0.04 g, 0.1 mmol) and Gd(O₂CMe)₃·6H₂O (0.03 g, 0.2 mmol) were simultaneously added to a solution of nancH₂ (0.037 g, 0.1 mmol) in MeOH/THF (8 mL, 3:1 mixture). The reaction mixture was left under magnetic stirring for approximately 1 h, until a dark brown solution was obtained. The solution was allowed to stand for ca. 16 h, filtered, and the resulting solution was allowed to undergo slow evaporation at room temperature, affording dark green crystals of 1 after 5 days. Yield 160 mg, 67% (based on the nancH₂ ligand). Selected IR data (cm⁻¹): 1614, 1594, 1568, 1532, 1495, 1462, 1445, 1423, 1400, 1375, 1300, 1193, 1175, 1163, 1142, 1095, 1078, 966, 929, 896, 860, 835, 816, 793, 760, 746, 696, 647, 622, 593, 582, 561, 541, 525, 502, 480, 455, 435, 418. Elemental Analysis calc. for [Cu^II(C₂₂H₁₃NO₃)]_n (1): C, 65.59; H, 3.25; N, 3.48. Found: C, 66.02; H, 3.48; N, 3.50%.

Single crystal X-ray diffraction: Suitable single crystals of 1 were mounted on a nylon microloop in perfluoroether oil (Paratone^® N). Crystallographic data were collected on a Bruker APEX-II CCD diffractometer equipped with an Oxford Cryosystems low-temperature device operating at 150.0(1) K. Generic φ and ω scans (MoKα, λ = 0.71073 Å) were used for the data measurement. The diffraction patterns were indexed, and the unit cells refined with SAINT software in the Bruker APEX-II program [66]. Data reduction, scaling, and a multi-scan absorption correction were performed with SAINT and SADABS software [67,68]. Space group determination was based upon analysis of systematic absences, E statistics, and successful refinement of all structures. The structure was solved using the intrinsic phasing algorithm ShelXT [69] and refined with the least squares method by minimization of Σw(F_o² − F_c²)²_. Structure refinement and CIF compilation were carried out using SHELXL-2018 in the SHELXTL package [70]. All non-hydrogen atoms were refined anisotropically. The positions of the hydrogen atoms were calculated geometrically and refined using the riding model. The crystallographic data for 1 was deposited in the Cambridge Structural Database and assigned the following number CCDC 2222531. Crystallographic data for 1 are summarized in Table 1.

Magnetic susceptibility: Variable temperature magnetic data (1.8–300 K) for 1 were collected using a Quantum Design MPMS-XL SQUID magnetometer, in a magnetic field strength of 1 kOe. Field-dependent magnetic data between 0 and 50 kOe were collected at 1.8 K with several data points recollected as the field returned to zero. No evidence for hysteresis was observed. Corrections for the sample holder assembly, measured independently, diamagnetic contributions from the sample, estimated from Pascal’s constants [71], and the temperature-independent paramagnetism (TIP) of Cu(II) were applied.

Computational Details: All calculations were carried out within the Jaguar 11.4 program package [72], using the B3LYP functional (Becke, three parameter, Lee−Yang−Parr hybrid functional) [73,74]. An a posteriori dispersion correction was applied using the D3 method of Grimme [75] and the LACV3P+** basis set employed [76], providing an effective core potential for the transition metal ion. A self-consistent field (1SCF) calculation was used based on a fragment of the polymer chain, comprising two Cu(II) ions, the bridging ligands, and the ligands in the immediate coordination sphere of each metal ion (Figure S1, Supplementary Materials). The strength of the exchange was determined to determine the energies and expectation values of the open shell spin triplet and broken symmetry singlet (BSS) configurations using the method of Yamaguchi (Equation (3)):

(3)$J=\frac{-(E_T-E_{BSS})}{<S^2{>}_T-<S^2{>}_{BSS}}$

The initial guess explicitly stated formal charges on the Cu(II) ions and O atoms of the nanc²⁻ ligands and the value of the spin state (2S) on each Cu(II) centre (either +1 for both Cu(II) centres for the triplet state or +1/−1 for the Cu(II) centres for the BSS configuration).

3. Results

Synthesis of nancH₂: The Schiff base ligand, nancH₂ (Figure 1), was obtained in 70% yield from the reaction of 2–hydroxy–1–naphthaldehyde and 3–amino–2–naphthoic acid, Scheme 1. The ligand was subsequently characterized by ¹H and ¹³C NMR, IR, and mass spectrometry (Figures S2, S3, S7 and S8).

Synthesis of complex 1: Cu(II)/Ln(III) coordination chemistry has been shown to provide 3d/4f metal complexes that possess high nuclearity, interesting magnetic properties, and unique structural topologies [77,78,79]. Accordingly, following the serendipitous self-assembly approach, various ligand/metal ratios were explored with nancH₂ and CuCl₂/GdCl₃, Cu(NO₃)₂/Gd(NO₃)₃, Cu(ClO₄)₂/Gd(CF₃SO₃)₃, and Cu(O₂CMe)₂/Gd(O₂CMe)₃ in both the presence and absence of Et₃N as the base. The reactions involving the CuCl₂/GdCl₃ and Cu(NO₃)₂/Gd(NO₃)₃ mixtures with nancH₂ led to a colour change, but no crystalline product(s) were isolated from the filtrate. The reactions of nancH₂ with Cu(ClO₄)₂/Gd(CF₃SO₃)₃ provided brown oils and/or yellow powder (attributed to unreacted nancH₂ ligand based on tlc and the ¹H NMR data). Numerous different Cu(O₂CMe)₂/Gd(O₂Cme)₃/nancH₂/Et₃N ratios were investigated, but again deposited nancH₂ as a yellow powder, indicating that the nancH₂ ligand was not coordinating to the metal ions. Conversely, in the absence of Et₃N, the room temperature reaction of Cu(O₂Cme)₂, Gd(O₂Cme)₃, and nancH₂, in a 1:2:1 ratio, afforded dark green crystals of 1 after several days which were found to be air stable. Although 1 does not contain Gd(III) ions, the presence of Gd(O₂CMe)₃ during the synthesis appeared crucial since attempts to isolate the Cu(II) coordination polymer 1 without the addition of a Gd(III) salt afforded no isolable products, both in the presence and absence of Et₃N. Similarly, the use of Gd(O₂Cme)₃ in a 1:1 ratio with Cu(O₂Cme)₂ also proved unsuccessful, confirming the need for a 1:2 ratio between these two metal salts. The Gd(III) ions may serve to deprotonate the nancH₂ ligand (especially in the absence of Et₃N) and/or abstract acetate from Cu(O₂Cme)₂, with formation of a [Gd(O₂Cme)₄]⁻ ‘ate complex, activating the Cu(II) centre with respect to attack by nancH_2.

Crystal structure of 1: Dark green crystals of 1 were obtained from reaction of Cu(O₂Cme)₂, Gd(O₂Cme)₃, and nancH₂ by slow evaporation of the mother liquor. Compound 1 crystalizes in the orthorhombic space group P2₁2₁2₁ with one Cu(nanc) unit in the asymmetric unit. The structure of the asymmetric unit, along with a portion of the polymer chain of 1, are presented in Figure 1. Selected bond distances and angles are listed in Table 2. In the asymmetric unit, a Cu(II) ion is coordinated by a doubly deprotonated nanc²⁻ ligand. A symmetry-related O3 atom completes the fourth coordination site, leading to a distorted square planar Cu(II) centre, where the sum of the angles (ranging from 87.21(9)–93.17(9)°, Table 2) is 363.76°. The distorted square planar geometry is further confirmed by the τ₄ descriptor for 4-coordination, which is 0.22 for 1, i.e., much closer to 0.00 for idealized square planar geometry than to 1.00 for tetrahedral [80]. The tetrahedrality calculated for complex 1 gives a dihedral angle of 22.67° (for strictly square planar complexes with D_4h symmetry the tetrahedrality is 0°; for tetrahedral complexes with D_2d symmetry the tetrahedrality equals 90°), again supporting a distorted square planar geometry for the basal CuO₃N plane [81]. The nanc²⁻ ligand and the Cu(II) centre are far from co-planar, as evidenced by the dihedral angles of 38.65° and 31.18° between the two naphthalene moieties of the nanc²⁻ ligand and the coordination plane of the Cu(II) ion. The molecule crystallizes in a chiral space group, with the polymer chains propagating parallel to the crystallographic a-axis. Neighbouring Cu1 ions are bridged via a carboxylato group that adopts a syn, anti-η¹:η¹:μ bidentate bridging mode, resulting in the formation of a 1D chain (Figure 1, bottom). This coordination mode provides a non-planar Cu1-O2-C22-O3-Cu1 bridge, and a Cu1⋯Cu1 intrachain distance of 4.902(5) Å. Detailed analysis of the crystal packing reveals there are no classical H-bonds, but there are C-H⋯π interactions involving an aromatic C-H donor of one molecule and an aromatic π-acceptor of a neighbouring molecule. For example, C-H⋯π distances for C-H(18)⋯Ar(C1C2C3C4C9C10) and C-H(15)⋯Ar(C12,C13,C14,C19,C20) were found to be 2.539 Å and 2.199 Å, respectively.

Magnetic properties of 1: M(H) measurements for 1 at 1.8 K revealed no hysteresis (Figure S6), consistent with previous observations that linear S = ½ chains do not show long-range order [82]. The saturation moment of 6300 emu/mol is consistent with an S = ½ ion with g-value of 2.2.

The variable temperature dc susceptibility data for 1 reveal the compound displays Curie–Weiss behaviour (45–300 K) with C = 0.474(1) Oe⁻¹ emu K mol⁻¹ and θ = +7.9(3) K (Figure 2, inset). The Curie constant is consistent with S = ½ and g = 2.248, while the positive Weiss constant is consistent with the presence of local ferromagnetic exchange. The value of χ_mT (Figure 2) at room temperature (0.484 emu K mol⁻¹ Oe⁻¹) is consistent with the Curie constant and increases upon cooling down to 1.8 K, in agreement with the positive nature of the Weiss constant. A first estimate of the exchange coupling can be derived from the mean field model which relates the microscopic exchange coupling (J) to the macroscopic Weiss constant (θ) according to Equation (4), where z = number of nearest neighbours, which is 2 for a linear chain. Based on Equation (4), a first estimate of J/k is +15.8 K (11 cm⁻¹):

θ = zJS(S + 1)/3k(4)

A more analytical approach to model the exchange within the polymer is to implement Equation (1) for the 1D quantum Heisenberg ferromagnetic chain model (1D QHFM), Equation (1) [30] which implements the H = −JS_i∙S_j Hamiltonian (Equation (2)). The fit to the 1D QHFM model is presented in Figure 2 (and Figure S5, Supporting Information). The best-fit provides an exchange parameter of J/k = +12.3 K and g = 2.271. The sign and magnitude of the exchange was also estimated using DFT on a model ‘dimer’ structure (Figure S1), extracted from the polymer chain which replicated the coordination environment of the two Cu(II) ions and the geometry of the bridging ligand.

DFT studies of 1: The strength of the exchange was also computationally determined at the B3LYP-D3/LACV3P*++ level of theory using Yamaguchi’s expression for the exchange (Equation (3)) [83,84], based on the computed energies and expectation values for the triplet and broken symmetry singlet configurations [85,86]. This afforded J/k = +13.8 K good agreement with that determined from fitting the magnetic data to the 1D QHFM model.

The syn, anti bridging mode has been identified to promote either weak ferromagnetic or antiferromagnetic exchange in carboxylato-bridged Cu(II) complexes [87]. However, as the Cu-O-C-O-Cu exchange pathway further deviates from planarity, the ferromagnetic contribution to the exchange parameter J is seen to increase, while the antiferromagnetic contribution is reduced, owing to the reduction in the overlap between the magnetic orbitals of the copper atoms via the syn, anti carboxylato group [88,89,90,91,92]. Thus, the non-planar Cu-O-C-O-Cu exchange pathway of 1 is consistent with the ferromagnetic behaviour revealed by the magnetic measurements.

4. Conclusions

A 1D Cu(II) polymer containing the new tetradentate Schiff base ligand, N-(2′-hydroxy-1′-naphthylidene)-3-amino-2-naphthoic acid (nancH₂) has been synthesized and magneto-structurally characterized. The molecular structure comprises distorted square planar Cu(II) ions linked via syn, anti- carboxylate bridges of the nanc²⁻ chelate. Analysis of the dc magnetic data reveals the presence of moderate ferromagnetic exchange interactions between the S = ½ metal centers. In this respect, the magnetic data fit well to a 1D quantum Heisenberg ferromagnetic (QHFM) chain with a g = 2.271 and J = +12.3 K. The experimental data are further supported by DFT calculations, where implementing the broken symmetry approach on a model dimeric unit extracted from the 1D chain, afforded an exchange coupling J = +13.8 K. These first preliminary results from the study of the coordination affinity of nanc²⁻ towards both 3d- and 4f-metal ions highlights the binding preference of nanc²⁻ for Cu(II) over Gd(III) ions. Work in progress is focused on the realization of this trend by employing different, redox-active, or inert 3d-metal ions and trivalent lanthanide ions.

Author Contributions

Conceptualization, M.P. and T.C.S.; investigation A.W., G.D.M., M.M.T., J.M.R. and M.P.; resources M.P. and M.M.T.; writing-original draft preparation, A.W., J.M.R. and M.P.; writing-review and editing, A.W., G.D.M., J.M.R., M.M.T. and M.P.; supervision, M.P. and J.M.R.; funding acquisition, J.M.R., M.M.T. and M.P. All authors have read and agreed to the published version of the manuscript.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The crystallographic data for 1 has been deposited in the Cambridge Structural Database and assigned the following number CCDC 2222531. It can be available for download free of charge at https://www.ccdc.cam.ac.uk/structures/ (accessed on 30 October 2022).

Conflicts of Interest

There are no conflict to declare.

Footnotes

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Figures, Scheme and Tables

Scheme 1. Synthesis of the Schiff base ligand, nancH2.

Figure 1. (top) ORTEP plot of the asymmetric unit of [CuII(nanc)]n (1) with the appropriate atomic labelling scheme. Thermal ellipsoids are plotted at 50% and H atoms are omitted for clarity; (bottom) crystal packing of 1, view down the crystallographic c-axis showing the 1-D chain topology; H atoms are omitted for clarity.

Figure 2. Temperature dependence of χmT for 1. The red solid line represents the best fit to the uniform Heisenberg 1D-ferromagnetic chain model. The inset displays the temperature dependence of 1/χm for 1. The red solid line represents the fit to the Curie–Weiss law (40–300 K).

Table 1

Selected crystallographic data for 1.

Chemical Formula	C22H13CuNO3
M r	402.87
Crystal system, space group	Orthorhombic, P212121
Temperature (K)	152(1)
a, b, c (Å)	7.3981 (5), 12.0652 (10), 18.5949 (13)
V (Å3)	1659.8 (2)
Z	4
Radiation type	Mo Kα
µ (mm−1)	1.34
Crystal size (mm)	0.5 × 0.5 × 0.5
Tmin, Tmax	0.561, 0.746
No. of measured, independent, andobserved [I > 2σ(I)] reflections	12654, 4985, 4680
R int	0.038
(sin θ/λ)max (Å−1)	0.715
R [F2 > 2σ(F2)], wR(F2), S	0.034, 0.076, 1.03
No. of reflections	4985
No. of parameters	245
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.49, −0.35
Absolute structure	Refined as an inversion twin.
Absolute structure parameter	0.081 (15)

Table 2

Selected geometric parameters (Å, º) for 1.

Cu1—O1	1.890 (2)	Cu1—O3i	1.947 (2)
Cu1—N1	1.933 (2)	O3—Cu1ii	1.9469 (19)
Cu1—O2	1.943 (2)
O1—Cu1—N1	92.29 (9)	O1—Cu1—O3i	87.21 (9)
O1—Cu1—O2	159.44 (10)	N1—Cu1—O3i	169.02 (9)
N1—Cu1—O2	93.17 (9)	O2—Cu1—O3i	91.09 (9)

Symmetry code(s): (i) x − ½, −y + ½, −z + 1; (ii) x + ½, −y + ½, −z + 1.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/chemistry5010007/s1, Figure S1: Structural model used for 1 when performing DFT calculations to elucidate the theoretical value of the magnetic exchange parameter J.; Figure S2. Infrared spectra obtained for the N-naphthalidene-2-amino-naphthoic acid (nancH2) ligand; Figure S3. Mass spectra obtained for the N-naphthalidene-2-amino-naphthoic acid (nancH2) ligand, in a DCM/MeOH solvent mixture; Figure S4. Infrared spectra obtained for 1; Figure S5. Temperature dependence of 1/χm for 1; Figure S6. Field/Temperature dependence of M for 1; Figure S7. 1H NMR spectrum of the N-naphthalidene-2-amino-naphthoic acid (nancH2) ligand in DMSO-d6; Figure S8. 13C NMR spectrum of the N-naphthalidene-2-amino-naphthoic acid (nancH2) ligand in DMSO-d6.

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