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1.
Dalton Trans ; 2020 Jun 12.
Artigo em Inglês | MEDLINE | ID: mdl-32530022

RESUMO

An alternative strategy for the synthesis of terpyridine based switchable molecular tweezers has been developed to incorporate anisotropic Mn(iii)-salphen complexes. The free ligand was synthesized using a building block strategy based on Sonogashira coupling reactions and was then selectively metalated with manganese in a last step. The conformation of the tweezers was switched from an open 'W' shaped form to a closed 'U' form by Zn(ii) coordination to the terpyridine unit bringing the two Mn-salphen moieties in close spatial proximity as confirmed by X-ray crystallography. An alternate switching mechanism was observed by the intercalation of a bridging cyanide ligand between the two Mn-salphen moieties that resulted in the closing of the tweezers. These dual stimuli are attractive for achieving multiple controls of the mechanical motion of the tweezers. A crystallographic structure of unexpected partially oxidized closed tweezers was also obtained. One of the two Mn-salphen moieties underwent a ligand-centered oxidation of an imino to an amido group allowing an intramolecular Mn-Oamide-Mn linkage. The magnetic properties of the manganese(iii) dimers were investigated to evaluate the magnetic exchange interaction and analyze the single molecule magnet behavior.

2.
Inorg Chem ; 2020 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-32538622

RESUMO

A series of four isomorphous, 1:2 (complex/L) rare cocrystals of coordination compounds of Ln(III) ions as [Ln(L)(NO3)3(H2O)]2[L]2 (Ln(III) = Gd (1), Tb (2), Dy (3), and Ho (4)), were synthesized with N,N-diisobutylisonicotinamide (L) using a metal-to-ligand ratio of 1:1. All compounds are dimeric in nature with two cocrystallized L molecules centro-symmetrically interspersed between two dimeric units with H-bonded bridges between them to form interesting, self-assembled H-bonded tapes along the c-axis. Detailed Shape analysis and Hirshfeld analysis are done to demonstrate geometry around the metal centers and various noncovalent interactions present in the systems, respectively. Magnetic studies show that compound 3 is a field-induced single-molecule magnet (SMM) for which the magnetization relaxes through a combination of Orbach (Δ = 51 K and τ0 = 3.1 × 10-7 s) and Raman mechanisms. Solid-state luminescence studies reveal that compounds 1, 2, and 3 are photoluminescent in the visible range, while 4 exhibits luminescence in the NIR region. Compound 3 shows cold white-light emission with Commission Internationale de l'Eclairage (CIE) coordinates (0.31, 0.30) and correlated color temperature (CCT) value of 6942 K.

3.
Dalton Trans ; 2020 Mar 25.
Artigo em Inglês | MEDLINE | ID: mdl-32211713

RESUMO

A family of mononuclear penta-coordinated CoII complexes, [Co(L)Cl2]·CH3OH (1), [Co(L)Br2] (2) and [Co(L)(NCS)2] (3) (where L is 1-mesityl-N,N-bis(pyridin-2-ylmethyl)methanamine) were synthesized and characterized. In these complexes, the neutral non-planar ligand, L, binds to three coordination sites around the metal center while two others are bound by anionic halide/pseudo halide ligands. The coordination geometry of the complexes is dictated by the coordinated anionic ligands. Thus, the coordination geometry around the metal ion is distorted trigonal bipyramidal for complexes 1 and 3, while it is distorted square pyramidal for complex 2. Ab initio CASSCF/NEVPT2 calculations on the complexes reveal the presence of an easy plane magnetic anisotropy with the D and E/D values being, 13.3 and 0.14 cm-1 for 1; 36.1 and 0.24 cm-1 for 2 and ±8.6 and 0.32 cm-1 for 3. These values are in good agreement with the values that were extracted from the experimental DC data. AC magnetic measurements reveal the presence of a field-induced slow relaxation of magnetization. However, clear maxima in the out-of-phase susceptibility curves were not observed for 1 and 3. For complex 2, peak maxima were observed when the measurements were carried out under an applied field of 1400 Oe which allowed an analysis of the dynamics of the slow relaxation of magnetization. This revealed that the relaxation is mainly controlled by the Raman and direct processes with the values of the parameters found to be: B = 0.77(15) s-1 K-6.35, n = 6.35(12) and A = 3.41(4) × 10-10 s-1 Oe-4 K-1 and m = 4 (fixed). The ab initio calculation which showed the multifunctional nature of the electronic states of the complexes justifies the absence of zero-field SIM behaviour of the complexes. The magnitude and sign of the D and E values and their relationship with the covalency of the metal-ligand bonds was analysed by the CASSCF/NEVPT2 as well as AILFT calculations.

4.
Molecules ; 25(3)2020 Jan 23.
Artigo em Inglês | MEDLINE | ID: mdl-31979347

RESUMO

The reaction between the 2,2'-benzene-1,4-diylbis(6-hydroxy-4,7-di-tert-butyl-1,3-benzodithiol-2-ylium-5-olate triad (H2SQ) and the metallo-precursor [Yb(hfac)3]2H2O led to the formation of a dinuclear coordination complex of formula [Yb2(hfac)6(H2SQ)]0.5CH2Cl2 (H2SQ-Yb). After chemical oxidation of H2SQ in 2,2'-cyclohexa-2,5-diene-1,4-diylidenebis(4,7-di-tert-butyl-1,3-benzodithiole-5,6-dione (Q), the latter triad reacted with the [Yb(hfac)3]2H2O precursor to give the dinuclear complex of formula [Yb2(hfac)6(Q)] (Q-Yb). Both dinuclear compounds have been characterized by X-ray diffraction, DFT optimized structure and electronic absorption spectra. They behaved as field-induced Single-Molecule Magnets (SMMs) nevertheless the chemical oxidation of the semiquinone to quinone moieties accelerated by a factor of five the relaxation time of the magnetization of Q-Yb compared to the one for H2SQ-Yb. The H2SQ triad efficiently sensitized the YbIII luminescence while the chemical oxidation of H2SQ into Q induced strong modification of the absorption properties and thus a quenching of the YbIII luminescence for Q-Yb. In other words, both magnetic modulation and luminescence quenching are reached by the oxidation of the protonated semiquinone into quinone.

5.
Chemistry ; 2020 Jan 13.
Artigo em Inglês | MEDLINE | ID: mdl-31943417

RESUMO

A textbook dysprosium dinuclear complex based on acetylacetone ligands, [Dy2 (acac)4 (µ2 -acac)2 (H2 O)2 ], has been synthesized and fully characterized. This simple dimeric lanthanide complex shows well-resolved solid-state luminescence and behaves as a single-molecule magnet under zero DC field. A seminal crystal-field approach is used to marry both magnetism and luminescence in the frame of an energetic picture.

6.
Chem Commun (Camb) ; 55(97): 14661-14664, 2019 Dec 18.
Artigo em Inglês | MEDLINE | ID: mdl-31746846

RESUMO

We report the first bromine-bridged dinuclear [Dy(Cy3PO)2(µ-Br)(Br)2]2·2C7H8 single-molecule magnet with an effective energy barrier of 684 K and magnetic hysteresis below 3 K. The asymmetric DyIII centres present two unique stereoisomeric octahedral coordination environments depending on the cis/trans disposition of the Cy3PO ligands, leading to the orthogonality of the easy magnetic axes that annihilates the dipolar interactions.

7.
Inorg Chem ; 58(16): 10725-10735, 2019 Aug 19.
Artigo em Inglês | MEDLINE | ID: mdl-31368683

RESUMO

Four new dinuclear complexes, [Co(µ-L)(µ-CCl3COO)Y(NO3)2]·2CHCl3·CH3CN·2H2O (1), [Co(µ-L)(µ-CH3COO)Y(NO3)2]·CH3CN (2), [Co(µ-L)(µ-PhCOO)Y(NO3)2]·3CH3CN·2H2O (3), and [Co(µ-L)(µ-tBuCOO)Y(NO3)2]·CHCl3·2H2O (4), having a CoIIYIII core, have been synthesized by employing a ferrocene based compartmental ligand which was synthesized by the reaction of diacetyl ferrocene with hydrazine hydrate followed by a condensation reaction with o-vanillin. A general synthetic protocol was employed to synthesize complexes 1-4, where the metallic core was kept the same with changing the bridging carboxylate groups. In all the complexes, the main structural motif is kept similar by only slightly varying the substitution on the bridging acetate groups. This variation has resulted in a small but subtle influence on the magnetic relaxation of all these four compounds. Ab initio CASSCF/NEVPT2 calculations were carried out to assess the effect of the different substitutions of the bridging ligands on the magnetic anisotropy parameters and on orbital arrangements. Ab initio calculations yield a very large positive D value, which is consistent with the geometry around the CoII ion and easy plane anisotropy (gxx, gyy > gzz), with the order of the calculated D in the range of 72.4 to 91.7 cm-1 being estimated in this set of complexes. To ascertain the sign of zero-field splitting in these complexes, EPR spectra were recorded, which support the sign of D values estimated from ab initio calculations.

8.
Inorg Chem ; 58(18): 11903-11911, 2019 Sep 16.
Artigo em Inglês | MEDLINE | ID: mdl-31192594

RESUMO

Four hexanuclear circular helicates, {[Dy6L6(DMF)12]·6CF3SO3·12DMF}2 (1Dy), {[Gd6L6(DMF)12]·6CF3SO3·12DMF}2 (1Gd), [Dy6L6(DMF)10(H2O)2]·6ClO4·4H2O·10DMF (2Dy), and [Gd6L6(DMF)12]·6ClO4·2H2O·10DMF (2Gd), where DMF = N,N-dimethylformamide, were synthesized by employing a glutaratedihydrazide-bridged bis(3-methoxysalicylaldehyde) ligand (H2L) and characterized structurally and magnetically. Direct-current magnetic susceptibility studies indicated predominant weak antiferromagnetic exchange interactions among gadolinium analogues, which were quantified using the PHI software, giving J = -0.003 cm-1 with g = 2.00 for 1Gd and J = -0.001 cm-1 with g = 2.02 for 2Gd. Alternating-current magnetic susceptibility measurements indicated that complexes 1Dy and 2Dy show slow relaxation of magnetization behavior, further supported by theoretical calculations that also highlighted the toroidal arrangement of the magnetic moments.

9.
J Chem Theory Comput ; 15(7): 4140-4155, 2019 Jul 09.
Artigo em Inglês | MEDLINE | ID: mdl-31125219

RESUMO

Complete and restricted active space self-consistent field (CAS-/RAS-SCF) wave function methods are applied for the calculation of circular dichroism (CD) and circularly polarized luminescence (CPL) of a series of molecules comprising four organic ketones, the chiral cobalt(III) complex [Co(en)3]3+, and the europium(III) complex [Eu(DPA)3]3-. The ab initio results are in good agreement with the experimental data and previous results obtained with Kohn-Sham density functional theory in the case of the spin-allowed transitions. CD and CPL properties are calculated ab initio for the spin-forbidden transitions of both a transition metal and a lanthanide complex.

10.
Dalton Trans ; 48(12): 3922-3929, 2019 Mar 19.
Artigo em Inglês | MEDLINE | ID: mdl-30816374

RESUMO

A centro-symmetric binuclear compound of formula [Dy(L)·(CH3COO)2·(H2O)2]2 (1) was isolated from the reaction between the 2,4-dinitrobenzoate anion (L) and the tris(acetate) of Dy(iii). Single crystal diffraction studies reveal a µ1-κ2,η1:η1 chelating binding mode of L while the binuclear compound is formed by the two bridging (µ2-κ3,η1:η2) acetate anions. The nona-coordinated sphere of each Dy(iii) ion is filled with a chelating (κ2,η1:η1) acetate anion and two terminal water molecules. Static magnetic measurements combined with ab initio SA-CASSCF/RASSI-SO calculations lead to two intramolecular competitive interactions i.e. ferromagnetic exchange interactions (0.04 cm-1) and antiferromagnetic dipolar interactions (-0.5 cm-1). Finally, dynamic magnetic measurements revealed a Single-Molecule Magnet behaviour in a zero-applied magnetic field with an effective energy barrier Δ = 21.5(2) cm-1 and τ0 = 7(3) × 10-6 s through Orbach and Quantum Tunnelling of the Magnetization relaxation mechanisms.

11.
Inorg Chem ; 58(4): 2872-2880, 2019 Feb 18.
Artigo em Inglês | MEDLINE | ID: mdl-30726073

RESUMO

The tailoring of the coordination chemistry around f-element centers is a crucial step for the development of compounds with slow magnetic relaxation, including single-molecule magnets (SMMs), which have great potential in molecular spintronics and for future quantum computing devices. Lanthanide ions are particularly interesting because the predominant electrostatic model of their bonding allows rationalizing their coordination symmetry. However, to the best of our knowledge, the redox properties of the lanthanides are not taken into account for the design of SMMs, and therefore all SMMs reported to date contain lanthanide ions in their trivalent oxidation state. In this Article, divalent lanthanide compounds presenting field-induced slow magnetic relaxation are reported. The rational design and synthesis of two TmII complexes with the 18-crown-6 ligand are presented along with their emission and EPR properties, which help to probe the desired nature of the ground state, that is, maximizing the anisotropy. The observed magnetic properties demonstrate their slow magnetic relaxation behavior in a moderate external magnetic field.

12.
Dalton Trans ; 48(6): 2135-2141, 2019 Feb 05.
Artigo em Inglês | MEDLINE | ID: mdl-30667435

RESUMO

The study of mononuclear lanthanide-based systems, where the observed Single Molecule Magnets (SMMs) properties originate from the local magnetic anisotropy of the single lanthanide ion, has been extensively investigated in the literature. The case for polynuclear lanthanide SMMs becomes more challenging both experimentally and theoretically due to the complexity of such architectures involving interactions between the magnetic centers. Much interest was devoted to the study of the structural effect on the magnetic interactions and relaxation dynamics. However, the understanding of the structural influence on those two factors remains a difficult task. To address this issue, a system containing two structurally related tetranuclear Dy(iii) SMMs, namely [Dy4(L)4(OH)2(DMF)4(NO3)2]·2(DMF)·(H2O) (1) and [Dy4(L)4(OH)2(DMF)2(NO3)2] (2) (H2L = 2-(2-hydroxy-3-methoxybenzylideneamino)phenol), is introduced and investigated. Through modifying the ligands on the changeable coordination sites, the intramolecular magnetic interactions and relaxation dynamics in these two Dy(iii)4 SMMs can be tuned. Both complexes exhibit slow relaxation of their magnetization with a relaxation barrier of 114 K for complex 2 while a blocking temperature below 2 K is observed for complex 1. Ab initio calculations reveal that changes in coordination numbers and geometries on the Dy(iii) sites can significantly affect the magnetic interactions as well as single-ion anisotropy. The combination of experimental work and ab initio calculations offers insight into the relationship between structures and magnetic properties and sheds light on the rational design of future polynuclear lanthanide SMMs with enhanced magnetic properties.

13.
Inorg Chem ; 58(1): 52-56, 2019 Jan 07.
Artigo em Inglês | MEDLINE | ID: mdl-30550268

RESUMO

The design of a coordination complex that involves a ligand combining both a tetrathiafulvalene core and a helicene fragment was achieved thanks to the reaction between the new 2-{1-[2-methyl[6]helicene]-4,5-[4,5-bis(propylthio)tetrathiafulvalenyl]-1 H-benzimidazol-2-yl}pyridine ligand (L) and the Dy(hfac)3·2H2O metalloprecursor. Magnetic investigations showed field-induced single-molecule-magnet (SMM) behavior under an applied magnetic field of 1000 Oe for [Dy(hfac)3(L)]·0.5CH2Cl2, while experimentally oriented single-crystal magnetic measurements allowed for determination of the magnetic anisotropy orientation. The magnetic behavior was rationalized through ab initio CASSCF/SI-SO calculations. This redox-active chiral-field-induced SMM paves the way for the design of switchable-multiproperty SMMs.

14.
Front Chem ; 6: 552, 2018.
Artigo em Inglês | MEDLINE | ID: mdl-30483497

RESUMO

Tetrathiafulvalene and 1,10-phenanthroline moieties present, respectively remarkable redox-active and complexation activities. In this work, we investigated the coordination reaction between the bis(1,10-phenanthro[5,6-b])tetrathiafulvalene triad (L) and the Dy(hfac)3·2H2O metallo precursor. The resulting {[Dy2(hfac)6(L)]·CH2Cl2·C6H14}3 (1) dinuclear complex showed a crystal structure in which the triad L bridged two terminal Dy(hfac)3 units and the supramolecular co-planar arrangement of the triads is driven by donor-acceptor interactions. The frequency dependence of the out-of-phase component of the magnetic susceptibility highlights three distinct maxima under a 2000 Oe static applied magnetic field, a sign that 1 displays a Single-Molecule Magnet (SMM) behavior with multiple magnetic relaxations. Ab initio calculations rationalized the Ising character of the magnetic anisotropy of the DyIII ions and showed that the main anisotropy axes are perpendicular to the co-planar arrangement of the triads. Single-crystal rotating magnetometry confirms the orientation of the main magnetic axis. Finally combining structural analysis and probability of magnetic relaxation pathways through Quantum Tunneling of the Magnetization (QTM) vs. excited states (Orbach), each DyIII center has been attributed to one of the three observed magnetic relaxation times. Such coordination compound can be considered as an ideal candidate to perform redox-magnetic switching.

15.
Angew Chem Int Ed Engl ; 57(52): 17089-17093, 2018 Dec 21.
Artigo em Inglês | MEDLINE | ID: mdl-30411438

RESUMO

Molecular materials that possess a toroidal moment associated to a non-magnetic ground state are known as single-molecule toroics (SMTs) and are usually planar molecules. Herein, we report a Dy4 cubane, namely [Dy4 (Bppd)4 (µ3 -OH)4 (Pa)4 (H2 O)4 ]⋅0.333 H2 O (where BppdH=1,3-Bis(pyridin-4-yl)propane-1,3-dione and PaH=2-Picolinic acid) for which magnetometry measurements and state-of-art ab initio calculations highlight SMT behavior in a tridimensional structure (3D-SMT). The in-depth theoretical analysis on the resulting low-lying energy states, along with their variation in function of the magnetic exchange pathways, allows further light to be shed on the description of single-molecule toroics and identify the coupling scheme that better reproduces the observed data.

16.
Inorg Chem ; 57(17): 11044-11057, 2018 Sep 04.
Artigo em Inglês | MEDLINE | ID: mdl-30130101

RESUMO

The rational design of molecular chains made of 4f ions and substituted 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radical is presented. The reaction of Ln(hfac)3·2H2O (hfac- = hexafluoroacetylacetonate) and the 4-cyano-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO-CN) radical affords air- and moisture-stable isostructural molecular chains of the formula [Ln(hfac)3TEMPO-CN] n for Ln = GdIII and TbIII, whereas zero-dimensional complexes of the formula [Dy(hfac)3(TEMPO-CN)2][Dy(hfac)3(H2O)2]2 are obtained for Ln = DyIII. To the best of our knowledge, the Gd derivative, Gd-TEMPO-CN, shows one of the strongest antiferromagnetic (AF) couplings for Gd-radical pairs ever reported with JGd-rad/ kB = -21.18 K, 14.72 cm-1 ( H = - JSrad SGd spin Hamiltonian convention). The TbIII derivative, Tb-TEMPO-CN, also shows strong Tb-radical AF coupling, which has been rationalized using the ab initio CASSCF approach ( JTb-rad = -23.02 K, -16.7 cm-1) and confirmed by luminescence measurements. Tb-TEMPO-CN shows remarkable properties for a Tb-radical-based single-molecule magnet ( Ueff = 69.3 ± 1 K; τ0 = 1.3 × 10-7 s) and two different relaxation processes triggered by interchain magnetic coupling.

17.
Inorg Chem ; 57(14): 8550-8557, 2018 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-29969252

RESUMO

The study of mononuclear lanthanide-based systems, where the observed single-molecule magnets (SMMs) properties originate from the local description of the magnetic properties of the lanthanide ion, has been widely investigated through the literature. The case of polynuclear SMMs becomes more challenging both experimentally and theoretically due to the complexity of such architectures involving interactions between the magnetic centers. Many efforts have been focused on the understanding of the nature of these interactions and their effects on the SMM properties. In this work, a series of three structurally related tetranuclear dysprosium(III) SMMs, namely, [Dy4(L)4(OH)2(DMF)4(NO3)2]·2(DMF)·(H2O) (1), [Dy4(L)4(OH)2(DMF)2(tfaa)2]·2(CH3CN) (2), and [Dy4(L)4(OH)2(DMF)2(acac)2]·2(DMF) (3) (H2L = 2-(2-hydroxy-3-methoxybenzylideneamino)phenol, Htfaa = trifluoroacetylactone, Hacac = acetylacetonate), has been synthesized and investigated. By a fine-tuning of the ligands on the changeable coordination sites in these Dy(III)4 SMMs, the intramolecular magnetic interactions can be modified, switching from antiferromagnetic (for 1 and 2) to ferromagnetic (for 3). Ab initio calculations support these statements. In addition, the formation of 1 has been analyzed by ESI-MS analysis of the reaction mixture, indicating rather quick and high-yield formation of the [Dy4] framework in solution. The combination of experimental work and ab initio calculations offers further insight into the relationship between structures and magnetic properties and sheds light on how to tune magnetic interactions in future polynuclear dysprosium complexes.

18.
Angew Chem Int Ed Engl ; 57(44): 14630-14634, 2018 Oct 26.
Artigo em Inglês | MEDLINE | ID: mdl-29981271

RESUMO

The paramagnetic cluster [Cu43 Al12 ](Cp*)12 was obtained from the reaction of [CuMes]5 and [AlCp*]4 (Cp*=η5 -C5 Me5 ; Mes=mesityl). This all-hydrocarbon ligand-stabilized M55 magic atom-number cluster features a Mackay-type nested icosahedral structure. Its open-shell 67-electron superatom configuration is unique. Three unpaired electrons occupy weakly antibonding jellium states. The situation prefigures the formation of a conduction band, which is in line with the measured temperature-independent magnetism. Steric protection by twelve Cp* ligands suppresses the intrinsic polyradicalar reactivity of the Cu43 Al12 core.

19.
Inorg Chem ; 57(8): 4534-4542, 2018 Apr 16.
Artigo em Inglês | MEDLINE | ID: mdl-29613778

RESUMO

Three mononuclear DyIII complexes with the same auxiliary ligand Lz (2,4-diamino-6-pyridyl-1,3,5-triazine), [Dy(TTA)3Lz] (1Dy) (TTA = 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionate), [Dy(acac)3Lz]·CH3OH·0.5H2O (2Dy) (acac = acetylacetonate), and [Dy(MQ)2Lz2]Br·CH3OH (3Dy) (HMQ = 2-methyl-8-quinolinol), have been synthesized through alteration of the ligands containing O donors. In all three complexes, the DyIII ions are eight-coordinate and submitted to pseudo- D4 d symmetry in the first coordination sphere. It is noteworthy that the TTA ligands in 1Dy are easily substituted by other bidentate capping ligands with O donors, leading to distinct magnetic properties, which were studied experimentally and via ab initio calculations. All three complexes were found to exhibit single-molecule magnet behavior with Ueff of 22 cm-1 (1Dy), 112 cm-1 (2Dy), and 56 cm-1 (3Dy) under zero applied dc field. Complex 1Dy demonstrates inferior SIM properties compared with 2Dy and 3Dy, which can be attributed to the strong electron-withdrawing effects of TTA ligands, as confirmed by theoretical calculations. However, butterfly-shaped magnetic hysteresis in 1Dy and 3Dy was observed at 1.9 K, while not in 2Dy.

20.
Dalton Trans ; 47(13): 4722-4732, 2018 Mar 26.
Artigo em Inglês | MEDLINE | ID: mdl-29537422

RESUMO

Single crystal diffraction studies reveal the formation of the following 10 new complexes of lighter Ln(iii) ions with general formulas {[Ln(µ2-L1)3·(H2O)2]·H2O}n (Ln = Nd (1) and Eu (2)), [Nd(µ2-L2)2·(CH3COO)·(H2O)2]n (3), [Ln2(µ2-L2)5·(L2)·(H2O)4]n (Ln = Sm (4), Ce (5), and Pr (6)), [La2(µ2-L2)6·(H2O)3·(DMF)]n (7) (DMF = dimethylformamide), [Ln(µ2-L2)2·(L2)·(H2O)3]2 (Ln = Eu (8) and Gd (9)) and [Gd(L2)·(CH3COO)2·(H2O)2]2 (10), where L1 and L2 are anions of 3,5- and 2,4-dinitrobenzoic acid, respectively. Complexes 1-7 are 1D coordination polymers, while 8-10 are dinuclear complexes. The luminescence properties of Nd(iii) and Eu(iii) analogues displayed metal-centred emission with L1 exhibiting weak but more efficient sensitization than L2. A study of the magnetic properties of the compounds clearly demonstrated the field-induced single ion magnet behaviour of the Nd(iii) compounds 1 and 3. Their behaviour has been compared to previously reported analogous Nd(iii) complexes and the role of the lattice solvent and polymorphism on the magnetic behaviour has been evaluated.

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