Synergetic Responses of Multiple Functions Induced by Phase Transition in Molecular Materials.

Materials that integrate magnetism, electricity and luminescence can not only improve the operational efficiency of devices, but also potentially generate new functions through their coupling. Therefore, multifunctional synergistic effects have broad application prospects in fields such as optoelectronic devices, information storage and processing, and quantum computing. However, in the research field of molecular materials, there are few reports on the synergistic multifunctional properties. The main reason is that there is insufficient awareness of how to obtain such material. In this brief review, we summarized the molecular materials with this characteristic. The structural phase transition of substances will cause changes in their physical properties, as the electronic configurations of the active unit in different structural phases are different. Therefore, we will classify and describe the multifunctional synergistic complexes based on the structural factors that cause the first-order phase transition of the complexes. This enables us to quickly screen complexes with synergistic responses to these properties through structural phase transitions, providing ideas for studying the synergistic response of physical properties in molecular materials.

Near-Room-Temperature Synergetic Response of Magnetism, Dielectricity and Luminescence Based on (C5 NH13 Cl)2 MnBr4.

Multifunctional materials with working temperatures near room temperature are crucial for practical applications. Until now, it is still a great challenge to obtain such materials. In this paper, a complex of (C5 NH13 Cl)2 MnBr4 (1) with a structural phase transition near room temperature is reported. The phase transition induces switchable magnetic properties, dielectric anomalies and luminescent response over the same range of temperatures. It is the first time the synergetic effect of magnetism, dielectricity and luminescence near room temperature have been observed in the same molecular complex.

Influence of the Different Types of Auxiliary Noncarboxylate Organic Ligands on the Topologies and Magnetic Relaxation Behavior of Zn-Dy Heterometallic Single Molecule Magnets.

In this work, we first synthesized a Zn-Dy complex, [Zn6Dy2(L)6(tea)2(CH3OH)2]·6CH3OH·8H2O (H2L = N-3-methoxysalicylidene-2-amino-3-hydroxypyridine, teaH3 = triethanolamine, 1), by employing H2L, anhydrous ZnCl2, and Dy(NO3)3·5H2O reacting with auxiliary ligand teaH3 in the mixture of CH3OH and DMF. When teaH3 and the solvent CH3OH in the reaction system of 1 were replaced by the auxiliary ligand 2,6-pyridinedimethanol (pdmH2) and the solvent MeCN, another Zn-Dy complex, [Zn4Dy4(L)6(pdm)2(pdmH)4]·10CH3CN·5H2O (2), was obtained. For 1, its crystal structure can be viewed as a dimer of two Zn3DyIII units. However, for 2, four DyIII form a zigzag arrangement, and each of its terminals linked two ZnII ions. Interestingly, although the structural topologies of 1 and 2 are different, the coordination geometries of DyIII in 1 and 2 are all triangular dodecahedron (TDD-8). The difference is that the continuous shape measure (CShM) values of DyIII in 1 are larger than the corresponding values in 2. Magnetic investigation revealed that the diluted sample 1@Y exhibits two magnetic relaxation processes, while 2 only exhibits a single relaxation process. Ab initio calculations indicated that, in the crystal lattice of 1, two complexes exhibiting slightly different CShM values of DyIII result in the double relaxation behavior of 1@Y. However, for 2, one of two DyIII fragments possesses a fast quantum tunneling of magnetization (QTM), resulting in its magnetic process presented at T < 1.8 K, so 2 exhibits single relaxation behavior. More importantly, the theoretical calculations also clearly indicated that the weak ligation at equatorial sites of DyIII in 1 and 2 ensure 1@Y and 2 possess SMM behavior, although the coordination geometry of DyIII (TDD-8) in 1 and 2 severely deviates from the ideal polyhedron and its axial symmetry is low.

Macrocyclic Chromium(III) Catecholate Complexes.

The synthesis and structural, electrochemical, spectroscopic, and magnetic characterizations of CrIII(HMC) catecholate and semiquinonate complexes are reported herein, where HMC is 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane. cis-[Cr(HMC)(Cat)]+ complexes (Cat = catecholate, [1]+; tetrachlorocatecholate, [2]+; and 3,5-di-tert-butylcatecholate, [3]+) were prepared from the reaction between appropriate catechol and [CrIII(HMC)Cl2]Cl reduced in situ by zinc. Chemical oxidation of [3]+ by FcPF6 resulted in cis-[Cr(HMC)(SQ)]2+ ([3]2+, SQ = 3,5-di-tert-butylsemiquinonate). Single crystal X-ray diffraction studies revealed the cis-chelation of the Cat/SQ ligand around the Cr metal center and confirmed the Cat/SQ nature of the ligands. Reversible oxidations of Cat to SQ were observed in the cyclic voltammograms of [1]+-[3]+, while the CrIII center remains redox inactive. The absorption spectrum of the SQ complex [3]2+ exhibits an intense spin-forbidden transition in solution. Time-delayed phosphorescence spectra recorded at 77 K revealed that all catecholate complexes emit from the 2E state, while [2]+ also emits from the 2T1 state. Temperature-dependent magnetic susceptibility measurements indicate the Cat complexes exist as S = 3/2 systems, while the SQ complex behaves as an S = 1 system, resulting from strong antiferromagnetic coupling of the S = 3/2 Cr center with the S = 1/2 SQ radical. Density functional theory (DFT) shows the similarities between the SOMOs of [1]+ and [2]+ and differences in their LUMOs in the ground state.

Narrow Band Gap Observed in a Molecular Ferroelastic: Ferrocenium Tetrachloroferrate.

Due to the intriguing chemical variability and structure-property flexibility, molecular materials with striking multifunctional characteristics, including tunable physical, chemical, optical, and electronic properties, have aroused wide attention. Recently, great advances have also been made in designing molecular ferroelastics with optoelectronic properties. However, the band gaps of the most typical ferroelastics are far in excess of 2.0 eV, which severely hinder their further applications. And this corresponds to the inherent incompatibility of ferroelastics. Herein we report an organometallic compound, ferrocenium tetrachloroferrate (1), undergoing a ferroelastic phase transition at 407.7 K with a large spontaneous strain of 0.1088. To the best of our knowledge, this is the first molecular ferroelastic with such a high Curie temperature (Tc) and narrow band gap of 1.61 eV. UV-vis absorption spectra and density-functional theory (DFT) calculation confirm this band gap. The band gap of 1 is determined by both the ferrocenium and the tetrachloroferrate components. The ideal semiconducting characteristic makes a breakthrough in the inherent incompatibility with ferroelastics. This will inspire an intriguing and further research in molecular ferroelastics with ideal semiconductor characteristics and hold great potential for the utilization in optoelectronic devices, especially the photovoltaic applications.

Exploring the Magnetic Interaction of Asymmetric Structures Based on Chiral VIII8 Clusters.

Polyoxovanadates (III) are important class of polyoxometalates in molecular magnetism field, and particularly the systems which contain vanadium(III) centers. To date, only very few highly reduced vanadium polynuclear complexes were reported, which remains a significant challenge to synthesize novel polyoxovanadates, owing to the characteristics of easily oxidized vanadium(III). Herein, two unprecedented petaloid chiral octanuclear polyoxovanadates, l- and d-[H2N(CH3)2]12.5(H3N(CH2)2NH3)(H3O)1.5(VIIIµ2-OH)8(SO4)16·2H2O (L-, D-V8), have been successfully obtained by solvothermal method without any chiral auxiliary. Both L- and D-V8 compounds contain the motif eight-membered ring (Vµ2-O)8(SO4)16 constituted of three different chiral entangled loops with the V atoms as nodes. Bond valence calculation (BVC) analysis indicates that all the V ions existed in L, D-V8 are +3 value. The magnetic behavior of compounds indicated ferromagnetic coupling between vanadium(III) ions. To our knowledge, it is the first chiral highly reduced polyoxovanadates that exhibit excellent ferromagnetism.

Polyoxometalate-Based Well-Defined Rodlike Structural Multifunctional Materials: Synthesis, Structure, and Properties.

The unpredictability of the polyoxometalate (POM) coordination model and the diversity of organic ligands provide more possibilities for the exploration and fabrication of various novel POM-based materials. In this work, a series of POM-based lanthanide (Ln)-Schiff base nanoclusters, [Ln(H2O)2(DAPSC)]2[Ln(H2O)3(DAPSC)]2[(SiW12O40)]3·15H2O (Ln = Sm, 1; Eu, 2; Tb, 3), have been successfully isolated by the reaction of classical Keggin POMs, a Ln3+ ion, and a Schiff-base ligand [2,6-diacetylpyridine bis(semicarbazone), abbreviated as DAPSC]. Both the hindrance effect of the organic ligand and charge balance endow the cluster with fascinating structural features of discrete and linear arrangement. The title compounds with dimensions of ca. 4 × 1 × 1 nm3 are first trimeric polyoxometalate-based nanosized compounds, constructed by saturated POM anions (SiW12O404-, denoted as SiW12). Moreover, the properties (stability, electrochemistry, third-order nonlinear optics, and magnetism) of the compounds have also been studied.

Exploring the Performance Improvement of Magnetocaloric Effect Based Gd-Exclusive Cluster Gd60.

Despite wide potential applications of Gd-clusters in magnetocaloric effect (MCE) owing to f7 electron configuration of Gd(III), the structural improvement in order to enhance MCE remains difficult. A new approach of the situ hydrolysis of acetonitrile is reported, and the slow release of small ligand CH3COO- is realized in the design and synthesis of high-nuclearity lanthanide clusters. A large lanthanide-exclusive cluster complex, [Gd60(CO3)8(CH3COO)12(µ2-OH)24(µ3-OH)96(H2O)56](NO3)15Br12(dmp)5·30CH3OH·20Hdmp (1-Gd60), was isolated under solvothermal conditions. To the best our knowledge, cluster 1 possesses the high metal/ligand ratio (magnetic density) and the largest magnetic entropy change (- Δ Smmax = 48.0 J kg-1 K-1 at 2 K for Δ H = 7 T) among previously reported high-nuclearity lanthanide clusters.

Important Role of Intermolecular Interaction in Cobalt(II) Single-Ion Magnet from Single Slow Relaxation to Double Slow Relaxation.

Two cobalt complexes with similar structures were synthesized using quinoline-2-carboxylic acid (HL) as the ligand. Both complexes are six-coordinated in antitriangular prism coordination geometries. There are one and four molecule units per cell for 1 and 2, respectively, with nearest Co-Co distances of 7.129 and 5.855 Å, respectively, which lead to their intermolecular interactions zj'. Both complexes are field-induced single-ion magnets. Complex 1 shows single slow relaxation under Hdc = 1.5 kOe attributed to the moment reversal, while complex 2 shows double slow relaxation resulting from intermolecular dipolar interaction and moment reversal, respectively.

Molecular ferroelectric with low-magnetic-field magnetoelectricity at room temperature.

Magnetoelectric materials, which encompass coupled magnetic and electric polarizabilities within a single phase, hold great promises for magnetic controlled electronic components or electric-field controlled spintronics. However, the realization of ideal magnetoelectric materials remains tough due to the inborn competion between ferroelectricity and magnetism in both levels of symmetry and electronic structure. Herein, we introduce a methodology for constructing single phase paramagnetic ferroelectric molecule [TMCM][FeCl4], which shows low-magnetic-field magnetoelectricity at room temperature. By applying a low magnetic field (≤1 kOe), the halogen Cl‧‧‧Cl distance and the volume of [FeCl4]- anions could be manipulated. This structural change causes a characteristic magnetostriction hysteresis, resulting in a substantial deformation of ~10-4 along the a-axis under an in-plane magnetic field of 2 kOe. The magnetostrictive effect is further qualitatively simulated by density functional theory calculations. Furthermore, this mechanical deformation significantly dampens the ferroelectric polarization by directly influencing the overall dipole configuration. As a result, it induces a remarkable α31 component (~89 mV Oe-1 cm-1) of the magnetoelectric tensor. And the magnetoelectric coupling, characterized by the change of polarization, reaches ~12% under 40 kOe magnetic field. Our results exemplify a design methodology that enables the creation of room-temperature magnetoelectrics by leveraging the potent effects of magnetostriction.

Single-molecule magnet behaviour in a centrosymmetric dinuclear dysprosium(III) complex: sequential differentiation of triple relaxation pathways.

A dinuclear complex with the formula Dy2L2(H2L)Cl2(EtOH)2 (Dy2) has been synthesized by reacting DyCl3·H2O with a ligand H2L (H2L = N,N'-ethylenebis(salicylideneimine)) using ethanol as the solvent. Its crystal structure can be viewed as a dimer of two Dy(III) fragments, where each Dy(III) site shows a N2O6Cl coordination sphere with a pentagonal bipyramid geometry (D5h). Magnetic measurements reveal that Dy2 behaves as a single-ion magnet (SIM) under a zero field. When the field is applied, the ac magnetic susceptibilities show double and triple peaks under high (≥600 Oe) and low (<600 Oe) dc fields, respectively. In contrast to the common double relaxation pathways in SIMs, such multiple and intricate relaxation pathways have not been reported yet in the previous literature. In this work, by experimental analysis of the ac signals, we attribute the three slow relaxation pathways to quantum tunnelling of magnetization (QTM), intermolecular dipole-dipole interaction and spin reversal, respectively. In addition, ab initio calculations are used to elucidate the magnetic behaviours of Dy2. Overall, our work indicates that the interpretation of the relaxation process using double relaxation pathways is incomplete and difficult in previously reported literature.

An Effective Strategy of Introducing Chirality to Achieve Multifunctionality in Rare-Earth Double Perovskite Ferroelectrics.

The hybrid rare-earth double perovskite (HREDP) system provides great convenience for the construction of multifunctional materials. However, suffering from the high symmetry of their intrinsic structure, HREDPs face the challenges in the realization and optimization of ferroelectric and piezoelectric properties. For the first time, after a systematic investigation of the chirality transformation principle, it is found that the introduction of chirality is an efficient strategy for the targeted construction of multifunctionality, which simultaneously increases the possibility of obtaining multiaxial ferroelectricity and ferroelasticity, and effectively realizes a large piezoelectric response. Moreover, chirality induced ferroelasticity will also achieve excellent magnetic or optical response driven by pressure-sensitive. To verify the feasibility of the above ideas, by using rare-earth ions (Ce3+ ) and suitable chiral organic cations, a new HREDP, (R-N-methyl-3-hydroxylquinuclidinium)2 RbCe(NO3 )6 (R1) is successfully designed, in which ferroelasticity, multiaxial ferroelectricity, satisfactory piezoelectric response, and the pressure-driven single-ion magnetics switch are simultaneously achieved for the first time. This work shows that the induction of chirality and the HREDP system provide an effective strategy and ideal platform for the expansion and optimization of the functions in perovskite ferroelectrics.

Reversible Switching of Single-Molecule Magnetic Behaviour by Desorption/Adsorption of Solvent Ligand in a New Dy(III)-Based Metal Organic Framework.

Two metal-organic frameworks (MOFs), [Dy(BDC)(NO3)(DMF)2] n (1, H2BDC = terephthalic acid) and [Dy(BDC)(NO3)] n (1a), were synthesized. The structures of MOFs 1 and 1a are easy to be reversibly transformed into each other by the desorption or adsorption of coordination solvent molecules. Accordingly, their magnetic properties can also be changed reversibly, which realizes our goals of manipulating on/off single-molecule magnet behaviour. MOF 1 behaves as a single-molecule magnet either with or without DC field. Contrarily, no slow magnetic relaxation was observed in 1a both under zero field and applied field.

A high-spin diradical dianion and its bridged chemically switchable single-molecule magnet.

Triplet diradicals have attracted tremendous attention due to their promising application in organic spintronics, organic magnets and spin filters. However, very few examples of triplet diradicals with singlet-triplet energy gaps (ΔE ST) over 0.59 kcal mol-1 (298 K) have been reported to date. In this work, we first proved that the dianion of 2,7-di-tert-butyl-pyrene-4,5,9,10-tetraone (2,7-tBu2-PTO) was a triplet ground state diradical in the magnesium complex 1 with a singlet-triplet energy gap ΔE ST = 0.94 kcal mol-1 (473 K). This is a rare example of stable diradicals with singlet-triplet energy gaps exceeding the thermal energy at room temperature (298 K). Moreover, the iron analog 2 containing the 2,7-tBu2-PTO diradical dianion was isolated, which was the first single-molecule magnet bridged by a diradical dianion. When 2 was doubly reduced to the dianion salt 2K2, single-molecule magnetism was switched off, highlighting the importance of diradicals in single-molecule magnetism.

Synthesis, crystal structures, HF-EPR, and magnetic properties of six-coordinate transition metal (Co, Ni, and Cu) compounds with a 4-amino-1,2,4-triazole Schiff-base ligand.

We have synthesized a series of transition metal compounds [M(L)2(H2O)2] (M = Co (1), Ni (2), and Cu (3)) by using the 4-amino-1,2,4-triazole Schiff-base ligand via the hydrothermal methods. They are all mononuclear compounds with the octahedral geometry. Direct-current magnetic and HF-EPR measurements were combined to reveal the negative D values (-28.78 cm-1, -10.79 cm-1) of complexes 1 and 2, showing the easy-axis magnetic anisotropies of compounds 1 and 2. Applying a dc field of 800 Oe at 2.0 K, the slow magnetic relaxation effects were observed in compound 1, which is a remarkable feature of single-ion magnets.

Optimal diamagnetic dilution concentration for suppressing the dipole-dipole interaction in single-ion magnets.

The effect of screening the CoII moment of monomeric [CoIIL2(H2O)] (L = 8-hydroxyquinaldine), having a trigonal bipyramid coordination, by diamagnetic Zn in CoxZn1-x solid solutions on its magnetic relaxation was explored using ac-susceptibility, high-field electron-spin-resonance measurements and CASPT2 calculations. The retention of the crystal structure for all the solid solutions was demonstrated using single crystal diffraction. The dc-magnetization and theoretical fittings of the susceptibility for Co1 and Co0.1Zn0.9 gave a large zero-field-splitting (ZFS) D of 50 ± 6 cm-1, and very weak dipole interaction between the nearest neighbors, while EPR and calculations confirmed the positive sign of the axial component (D). Consistent parameters were obtained from experiments and theory. Importantly, only field-induced relaxation was observed for the samples with less than 50% Co and a gradual change in the barrier energy to moment reversal and relaxation times was observed between 11% and 20% Co, while both were enhanced for higher dilutions. The results establish a clear barrier for extending the longevity of the magnetism for this type of single-ion species by lowering the intramolecular interactions. The results suggest that the magnetic interaction persists up to the second sphere, that is, for a dilution of 1 in 9 (11% Co). Importantly, this method is applicable to all single-ion magnet systems, that is, the optimum dilution concentration to restrain the dipole field can be given only by the single crystal structure.

Structurally modulated single-ion magnets of mononuclear ß-diketone dysprosium(III) complexes.

Five ß-diketone based Dy(iii) single-ion magnets (SIMs), [DyIII(TTA)3(AIP)]·0.5CH3CH2OH·0.5H2O (1), [DyIII(TTA)3(APIP)]·2CH3OH·H2O (2), [DyIII(TTA)3(DPP)] (3), [DyIII(TTA)3(BPP)]·0.5CH3CH2OH (4) and [DyIII(TTA)3(AIP)]·1.5H2O (5), were fully synthesized through alteration of their phenanthroline derivates (AIP = 2-(anthracen-9-yl)-1H-imidazo[4,5-f][1,10]phenanthroline, APIP = 2-(4-(anthracen-9-yl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, DPP = 2,3-diphenylpyrazino[2,3-f][1,10]phenanthroline and BPP = 2,3-bis(2,5-dimethylthiophen-3-yl)pyrazino[2,3-f][1,10]phenanthroline). Magnetic investigations reveal that all the complexes perform as SIMs, with notably different effective barriers of 69.4 K (1), 147.3 K (2), 122.1 K (3) and 234.2 K (4) in zero direct current (dc) field. Complexes of 2 and 4 possess almost twofold higher effective barriers compared to 1 and 3. By analyzing the crystal structures, the distinct magnetic dynamics was found to stem from the variation in intermolecular hydrogen bond interactions and charge delocalization of auxiliary ligands. With the help of ab initio calculations, a change of auxiliary ligand brings about varying intensities of quantum tunnelling magnetization (QTM), which account for the distinguishable magnetic dynamics. With a combination of experimental and theoretical analyses, this work provides a visual and instructive perspective to the understanding of fine tuning auxiliary ligands to design structurally modulated SIMs of mononuclear ß-diketone dysprosium(iii) complexes.

Light-controlled efficient photoluminescence based on an europium ß-diketonate complex with single-crystal-to-single-crystal [2+2] cycloaddition.

A brand new europium(iii) ß-diketonate complex undergoes a single-crystal-to-single-crystal transformation via [2+2] cycloaddition after UV irradiation, triggering strong Eu(iii) red emission turn-on, which is highly photostable even after 50 hours of irradiation. A photo-patterning process is successfully conducted for security printing application in materials science.

Synthesis, crystal structures and magnetic properties of a series of chair-like heterometallic [Fe4Ln2] (Ln = GdIII, DyIII, HoIII, and ErIII) complexes with mixed organic ligands.

Four chair-like hexanuclear Fe-Ln complexes containing mixed organic ligands, namely, [Fe4Ln2{(py)2CO2}4(pdm)2(NO3)2(H2O)2Cl4]·xCH3CN·yH2O (Ln = GdIII (1, x = 1, y = 0), DyIII (2, x = 1, y = 1), HoIII (3, x = 0, y = 2), and ErIII (4, x = 1, y = 3); (py)2CO2H2 = the gem-diol form of di-2-pyridyl ketone and pdmH2 = 2,6-pyridinedimethanol) have been obtained by employing di-2-pyridyl ketone and 2,6-pyridinedimethanol reacting with FeCl3 and Ln(NO3)3 in MeCN. The structures of 1-4 are similar to each other except for the number of lattice solvent molecules. Four FeIII and two LnIII in these complexes comprise a chair-like core with the "body" constructed by four FeIII ions and the "end" constructed by two LnIII ions. Among the four compounds, 2 shows field-induced single molecule magnet behavior as revealed by ac magnetic susceptibility studies, with the effective energy barrier and the pre-exponential factor of 22.07 K and 8.44 × 10-7 s, respectively. Ab initio calculations indicated that, among 2_Dy, 3_Ho and 4_Er fragments, the energy gap between the lowest two spin-orbit states for 2_Dy is the largest, while the tunneling gap for 2 is the smallest. These might be the reasons for complex 2 exhibiting SMM behavior. Additionally, the orientations of the magnetic anisotropy of DyIII in 2 were obtained by electrostatic calculations and ab initio calculations, both indicating that the directions of the main magnetic axis of Dy1 ions are almost aligned along Dy1-O5 (O5 from the pdm2- ligand).

Single molecule magnet behaviors of Zn4Ln2 (Ln = DyIII, TbIII) complexes with multidentate organic ligands formed by absorption of CO2 in air through in situ reactions.

In this work, we report the syntheses, crystal structures and magnetic properties of three novel Zn-Ln mixed metal complexes, namely [Zn4Dy2(L1)2(L2)2(N3)2]Cl2·2H2O (1), [Zn4Tb2(L1)2(L2)2(Cl)2][ZnN3Cl3]·2H2O (2), and [Zn4Gd2(L1)2(L2)2(Cl)2][ZnN3Cl3]·2H2O (3), in which L12- and L23- were formed from the ligand L [L = N1,N3-bis(3-methoxysalicylidene)diethylenetriamine] through in situ reactions. Interestingly, carbon dioxide in air was absorbed in the process of forming carbamate ligand L23-; this can be ascribed to the insertion of CO2 into M-N amide bonds. Moreover, 1 and 2 represent the first series of 3d-4f SMMs containing carbamate ligands by fixation of CO2 in air. Single-crystal X-ray diffraction analyses reveal that the crystal structures of 1 and 2 are anion-dependent, i.e., the apical positions of the two ZnII ions in 1 and 2 are occupied by an N atom of N3- and by Cl-, respectively. However, the topologies of 2 and 3 are similar. Two ZnII ions and one LnIII (Ln = Dy (1), Tb (2) and Gd (3)) form nearly linear trinuclear [Zn2Ln] units which are double-bridged by two L23- ligands. Magnetic studies reveal that two complexes show single molecule magnet behavior under a direct current (dc) field, with effective energy barriers (Ueff) of 30.66(5) K for 1 and 8.87(3) K for 2. Ab initio calculations reveal that the DyIII ions in 1 and the TbIII ions in 2 are axial in nature; however, a difference in the tunnel splitting of 1 and 2 leads to variation in the magnetization blockades of the two complexes. Theoretical calculations also indicate that the directions of the main magnetic axes severely deviate from the coordination atoms of the first spheres of DyIII and TbIII in 1 and 2; thus further results in poor SMM behavior of the two complexes.