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.

Indeno[2,1-a]fluorene-11,12-dione Radical Anions: Synthesis, Characterization, and Properties.

The one-electron reduction of indeno[2,1-a]fluorene-11,12-dione (IF) with various alkali metals prepare the radical anion salts. The data about different structures, properties, and characterization was obtained by single-crystal X-ray diffraction, electron paramagnetic resonance (EPR) spectroscopy, superconducting quantum interference device (SQUID) measurements, and physical property measurement system (PPMS). Compound IF.- K+ (18-c-6) is regarded as a one-dimensional magnetic chain through C-H⋅⋅⋅C interaction. Theoretical calculations and magnetic results showed that [IF.- K+ (15-c-5)]2 is a dimer with an open-shell ground state. Compounds IF.- Na+ (15-c-5) and IF.- K+ (cryptand) are monoradical anion salts: IF2 .- Li+ possesses unique π-stack structure with an interplanar separation less than 3.46 Å, making it a semiconductor (δRT =1.9×10-4  S ⋅ cm-1 ). This work gives insights into multifunctional radical anions, and describes the design and development of different functional radicals.

Significantly Enhancing the Single-Molecule-Magnet Performance of a Dinuclear Dy(III) Complex by Utilizing an Asymmetric Auxiliary Organic Ligand.

In this work, we employed an asymmetric auxiliary organic ligand (1,1,1-trifluoroacetylacetone, Htfac) to further regulate the magnetic relaxation behavior of series of Dy2 single-molecule magnets (SMMs) with a N1,N3-bis(3-methoxysalicylidene)diethylenetriamine (H2L) ligand. Fortunately, an air-stable Dy2 complex, [Dy2(L)2(tfac)2] (1; Htfac = 1,1,1-trifluoroacetylacetone) was obtained at room temperature. A structural analysis indicated that some Dy-O or Dy-N bond lengths for 1 are not in the range of those for the complexes [DyIII2(L)2(acac)2]·2CH2Cl2 (Dy2-acac; Hacac = acetylacetone) and [DyIII2(L)2(hfac)2] (Dy2-hfac; Hhfac = hexafluoroacetylacetone), although the electron-withdrawing ability of tfac- is stronger than that of acac- but weaker than that of hfac-. Additionally, the Dy-O3/O3a (the two O atoms bridged to DyIII ions) bond lengths are also affected by the asymmetrical Htfc ligand. This indicated that the charge distribution of the coordination atoms around DyIII has been modified in 1, which leads to the fine-tuning of the magnetic relaxation behavior of 1. Magnetic studies indicated that the values of effective energy barrier (Ueff) for 1 and its diluted sample (2) are 234.8(3) and 188.0(6) K, respectively, which are both higher than the reported value of 110 K for the complex Dy2-hfac. More interestingly, 1 exhibits a magnetic hysteresis opening when T < 2.5 K at zero field, while the hysteresis loops of 2 are closed at a zero dc field. This discrepancy is due to the weak intramolecular exchange coupling in 2, which cannot overcome the QTM of the single DyIII ion. Ab initio calculations for 1 revealed that the charge distributions of the coordination atoms around DyIII ions were regulated and the intramolecular exchange coupling was indeed improved when the asymmetrical Htfc was employed as a ligand for the synthesis of this kind of Dy2 SMM.

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.

Guest-Induced Switching of a Molecule-Based Magnet in a 3d-4f Heterometallic Cluster-Based Chain Structure.

With the motivation of controlling a magnetic switch by external stimuli, we report here an infinite chain structure formed from the secondary building units of Cu3Tb2 clusters through the linkage of nitrate ions. It behaves as a molecule-based magnet with the highest energy barrier among isolated Tb/Cu-based single-molecule magnets and single-chain magnets, which is close to a dimer of a Cu3Tb2 cluster unit from a magnetic point as revealed by its correlation length of 2.23 Cu3Tb2 units. This kind of molecule-based magnet in a chain structure is rare. The removal of its guest ethanol molecules leads to the complete disappearance of slow magnetic relaxation behavior. Interestingly, the capture and removal of guest ethanol molecules are reversible, mediating a rare ON/OFF switching of a 3d-4f heterometallic molecule-based magnet, which was interpreted by the theoretical calculations based on the structural difference upon desolvation.

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.

Isolable Lanthanide Metal Complexes of a Phosphorus-Centered Radical.

Reaction of the diazafluorenylidene-substituted phosphaalkene 1 with [Cp*2Ln][BPh4] (Ln = Dy, Tb, and Gd), followed by subsequent reduction with KC8, afforded complexes Cp*2Dy(N,N'-1) (2), Cp*2Tb(N,N'-1) (3), and Cp*2Gd(N,N'-1) (4) in moderate yields, in which the phosphaalkene moiety is in the radical-anion state. Complexes 2 and 3 represent the first lanthanide metal complexes of a heavy main-group element-based radical. They have been characterized by single-crystal X-ray diffraction, UV/vis spectroscopy, and superconducting quantum interference device measurements. The magnetic studies reveal that the phosphorus-radical centers have a quite weak antiferromagnetic interaction with the lanthanide ions in 2-4. Furthermore, complex 2 shows slow magnetic relaxation behavior.

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 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.

Two Dy(III) Single-Molecule Magnets with Their Performance Tuned by Schiff Base Ligands.

To develop new lanthanide single-molecule magnets (SMMs), two new complexes of [Dy2(MeOH)2(HL1)2(NO3)2]·2MeOH (1) and [Dy6(µ3-OH)2(L2)2(HL2)2(H2L2)2Cl2(EtOH)2]Cl2·3EtOH·CH3CN (2) were obtained by reacting Dy(NO)3·6H2O with 3-amino-1,2-propanediol in the presence of 2-hydroxynaphthaldehyde for 1 and by reacting DyCl3·6H2O with 1,1-di(hydroxymethyl)ethylamine in the presence of 2-hydroxynaphthaldehyde for 2, respectively, in which the Schiff base ligands of 3-(((2-hydroxynaphthaen-1-yl)methylene)amino)-propane-1,2-diol (H3L1) and 2-(ß-naphthalideneamino)-2-(hydroxylmethyl)-1-propanol (H3L2) were in situ formed. The two Dy(III) ions in 1 are linked by two Oalkoxy atoms of two (HL1)2- ligands to build a dinuclear skeleton. Complex 2 presents a nearly planar hexanuclear skeleton constructed from four edge-shared triangular Dy3 units with the two peripheral Dy3 units consolidated by two µ3-O bridges and the two central Dy3 units consolidated by one µ3-O bridge. Obviously, they exhibit a different topological arrangement resulting from the linkage of the Schiff base ligands. Both of them are typical SMMs under zero dc fields, with a Ueff/ kB value of 34 K for 1 and 40 K for 2, respectively. Multiple processes are involved in the relaxation processes of 1 and 2. The different SMM performances of the two titled complexes reveal a tuning effect of Schiff base ligands through tuning the coordination environments and topological arrangements of dysprosium(III) ions, which is supported by the theoretical calculations.

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.

A Multiferroic Spin-Crossover Molecular Crystal.

Spin-crossover (SCO) ferroelectrics with dual-function switches have attracted great attention for significant magnetoelectric application prospects. However, the multiferroic crystals with SCO features have rarely been reported. Herein, a molecular multiferroic Fe(II) crystalline complex [FeII(C8-F-pbh)2] (1-F, C8-F-pbh = (1Z,N'E)-3-F-4-(octyloxy)-N'-(pyridin-2-ylmethylene)-benzo-hydrazonate) showing the coexistence of ferroelectricity, ferroelasticity, and SCO behavior is presented for the first time. By H/F substitution, the low phase transition temperature (270 K) of the non-fluorinated parent compound is significantly increased to 318 K in 1-F, which exhibits a spatial symmetry breaking 222F2 type ferroelectric phase transition with clear room-temperature ferroelectricity. Besides, 1-F also displays a spin transition between high- and low-spin states, accompanied by the d-orbital breaking within the t2g 4eg 2 and t2g 6eg° configuration change of octahedrally coordinated FeII center. Moreover, the 222F2 type ferroelectric phase transition is also a ferroelastic one, verified by the ferroelectric domains reversal and the evolution of ferroelastic domains. To the knowledge, 1-F is the first multiferroic SCO molecular crystal. This unprecedented finding sheds light on the exploration of molecular multistability materials for future smart devices.

A cationic sulfur-hydrocarbon triradical with an excited quartet state.

The triptycene-bridged tris(thianthrene) compound 1 was designed and synthesized. Three-electron oxidation of 1 by NO[Al(OC(CF3)3)4], followed by crystallization at two different temperatures resulted in the triradical trication salts 2a and 2b respectively, which feature different crystal packing patterns. The triradical trications in 2a and 2b both feature a doublet ground state which can be thermally populated to a quartet state, representing the first examples of cationic main-group triradicals.

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.

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.