Antiprismatic Coordination Research Articles

Chiral Homodinuclear Dysprosium Macrocyclic Complexes with Single‐Molecule Magnetic Behaviours

AbstractA pair of enantiomerically chiral dysprosium homodinuclear complexes: [(acac)4Dy2(R,R,R,R‐L)] (R‐Dy) and [(acac)4Dy2(S,S,S,S‐L)] (S‐Dy) (Hacac=acetylacetone) have been synthesized based on macrocyclic chiral ligands (R,R,R,R‐H2L or S,S,S,S‐H2L), derived from the [2+2] template condensation of 4‐tert‐butyl‐2,6‐diformylphenol, dysprosium acetylacetonate and (1R,2R)‐/(1S,2S)‐1,2‐cyclohexanediamine, respectively. Circular dichroism spectra confirms their enantiomeric chirality. Single‐crystal structures show two crystallographic independent dysprosium(III) ions have square antiprismatic coordination with different D4d local symmetry. Furthermore, the selected R‐Dy complex owns the slow magnetic relaxation behaviour with the ferromagnetic Dy3+⋅⋅⋅Dy3+ coupling.

Synthesis, characterization, crystal structures and biological activity of 4-chloro-2-(2-hydroxy-3-ethoxybenzylideneamino)phenol and complexes

Molecular nanoclusters comprising a heterometallic 3d-4f stoichiometry are an interesting class of compounds. In this paper, a chloro-containing Schiff base 4-chloro-2-(2-hydroxy-3-ethoxybenzylideneamino)phenol (H2L) was prepared by condensation reaction of 3-ethoxysalicylaldehyde with 2-amino-4-chlorophenol in methanol. The Schiff base is predisposed to chelate within a cluster core both 3d and 4f metal ions. Reaction of H2L with nickel salts afforded a tetranuclear NiII complex [Ni4L4(MeOH)4] (1), while with nickel salts and lanthanide(III) nitrate three tetranuclear NiII-LnIII complexes [Ni2Eu2L4(NO3)2(DMF)2] (2), [Ni2Er2L4(NO3)2(DMF)2] (3), [Ni2Tb2L4(CH3COO)2(DMF)2]·4DMF (4) were obtained. H2L and the complexes have been characterized by elemental analysis, IR, UV–Vis spectra. H2L has also been characterized by 1H and 13C NMR spectra. Molecular structures of the compounds have been determined by single crystal X-ray determination. In the complexes, the Schiff base ligands coordinate to the metal atoms via ether oxygen, imino nitrogen and two phenolate oxygen atoms. All the Ni atoms in the complexes are in octahedral coordination. The rare earth metal atoms are eight coordinated by the phenolate and ether oxygen of the Schiff base ligands, and anionic and solvent oxygen atoms, forming square antiprismatic coordination. The compounds were evaluated for their antibacterial activities on Bacillus subtilis, Staphylococcus aureus, Escherichia coli and Pseudomonas fluorescens, and antifungal activities on Candida albicans and Aspergillus niger, and gave interesting results.

Structures, photoluminescence, and magnetism of 1D lanthanide coordination polymers dominated on 3,5‐dichlorobenzoate

AbstractTwo series of novel coordination polymers (CPs), namely, Ln3(3,5‐DCB)9(bipy) (H2O)2·(bipy) [Ln = Nd (1), Sm (2)] and Ln2(3,5‐DCB)6(bipy)H2O [Ln = Eu (3), Gd (4), Tb (5) and Dy (6)], have been synthesized by hydrothermal reaction of a bridging ligand, 3,5‐dichlorobenzoic acid (3,5‐HDCB), with LnCl3·nH2O and N‐donor neutral ligand, 2,2′‐bipyridine (bipy). Single‐crystal x‐ray diffraction, elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), and powder x‐ray diffraction (PXRD) for 1–6 are presented. CPs 1 and 2 exhibit trinuclear lanthanide architectures, in which the center Ln(III) are seven‐coordinated and eight‐coordinated adopting monocapped triangular prismatic, distorted square antiprism and bicapped trigonal prismatic coordination geometry, respectively, whereas CPs 3–6 are isostructural dinuclear structures. The center Ln(III) ions are also seven‐coordinated and eight‐coordinated with different coordinate modes adopting distorted monocapped triangular prismatic and square antiprism coordination geometry. Trinuclear CPs 1 and 2 are packed together via hydrogen‐bonding interaction to form the two‐dimensional (2D) supramolecular layers. CPs 3–6 exhibit 2D layers by the π–π interaction. CPs 2, 3, 5, and 6 display the characteristic fluorescent emissions of Sm(III), Eu(III), Tb(III), and Dy(III), respectively. CPs 1 and 4–6 exhibit corresponding weak anti‐ferromagnetic and ferromagnetic interactions of Nd(III), Gd(III), Tb(III), and Dy(III) in the low‐temperature range.

Decoration of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) with N-oxides increases the T1 relaxivity of Gd-complexes.

High complex stability and longitudinal relaxivity of Gd-based contrast agents are important requirements for magnetic resonance imaging (MRI) because they ensure patient safety and contribute to measurement sensitivity. Charged and zwitterionic Gd3+-complexes of the well-known chelator 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) provide an excellent basis for the development of safe and sensitive contrast agents. In this report, we describe the synthesis of DOTA-NOx, a DOTA derivative with four N-oxide functionalities via "click" functionalization of the tetraazide DOTAZA. The resulting complexes Gd-DOTA-NOx and Eu-DOTA-NOx are stable compounds in aqueous solution. NMR-spectroscopic characterization revealed a high excess of the twisted square antiprismatic (TSAP) coordination geometry over square antiprismatic (SAP). The longitudinal relaxivity of Gd-DOTA-NOx was found to be r1=7.7 mm-1 s-1 (1.41 T, 37 °C), an unusually high value for DOTA complexes of comparable weight. We attribute this high relaxivity to the steric influence and an ordering effect on outer sphere water molecules surrounding the complex generated by the strongly hydrated N-oxide groups. Moreover, Gd-DOTA-NOx was found to be stable against transchelation with high excess of EDTA (200 eq) over a period of 36 h, and it has a similar in vitro cell toxicity as clinically used DOTA-based GBCAs.

Tuning the slow magnetic relaxation with the substituents in anilate bridged bis(dysprosium) complexes.

Dinuclear lanthanide complexes [((HB(pz)3)2Dy)2(μ-Th2An)] (1Dy) and [((HB(pz)3)2Dy)2(μ-ClCNAn)] (2Dy), based on the hydrotris(pyrazol-1-yl)borate (HBpz3-) scorpionate capping ligand and anilate (An2-) bridging linkers, namely homosubstituted dithiophene- and heterosubstituted chlorocyanoanilate, bearing electron-donating and withdrawing substituents at the 3,6-positions of the benzoquinone core, are reported. 1Dy shows an octacoordinated {N6O2} DyIII ion within a D4h distorted square antiprismatic coordination, an ideal geometry for Single-Molecule Magnet (SMM) behavior, given its oblate nature, whereas in 2Dy the octacoordinated DyIII ion adopts a D2d triangular dodecahedron geometry, while maintaining the same {N6O2} coordination sphere. Both complexes show field-induced single molecule magnet (SMM) behaviour, with tuning of the slow magnetic relaxation as a function of the nature of the substituents at the 3,6-positions of the anilate moiety. A comparison of the Arrhenius fitting parameters for 1Dy and 2Dy supports the hypothesis that square antiprismatic DyIII complexes, as 1Dy, exhibit higher energy barriers. This interpretation is supported by ab initio calculations that also shed light on the crucial role of intermolecular dipolar interactions.

Structure and mobility of rare earth ions in interlayer space of montmorillonite: a molecular dynamics study.

Ion adsorption-type deposits (IADs) are the dominant sources of rare earth elements (REEs), in which REEs are mainly enriched in clay minerals. However, the adsorption mechanism of REEs in the interlayer region of clay minerals is still poorly understood. In this study, by using molecular dynamics (MD) simulations, we explored the interlayer structures and dynamics of REEs-intercalated montmorillonite. La3+ and Lu3+ were used as the model cations for light REEs (LREEs) and heavy REEs (HREEs), respectively. It was found that the most thermodynamically stable state for both LREE- and HREE-montmorillonite was the double-hydration state and the corresponding basal spacing was calculated to be ∼16.1 Å. REE ions are located at the middle plane of the interlayer space and adsorbed on the montmorillonite basal surface through hydrogen bonds between its coordination water and the basal oxygens (i.e. as outer-sphere complexes). La3+ was 9-fold coordinated in the interlayer space with a mono-capped square antiprism coordination shell, while Lu3+ was 8-fold coordinated in a square antiprism cage. The mobility of REEs intercalated in the interlayer was significantly reduced compared to the mobility of REEs in aqueous solutions. The microscopic structures, thermodynamic data, and mobility obtained in the present study can help understand the enrichment and mobilization of REEs in IADs, and provide a molecular level basis for developing more efficient extraction techniques.

Highly selective recovery of yttrium from mining wastewater using biosynthetic iron sulfide nanoparticles

The selective recovery of rare earth elements (REEs) from mining wastewater has become a hot research topic due to the increasing industrial value of REEs. Herein, biosynthetic iron sulfide nanoparticles (nFeS) were deployed as a superior adsorbent to selectively recover Y(Ⅲ) from mining wastewater. The maximum adsorption efficiency achieved for of Y(Ⅲ) by nFeS was 81.2 % compared to only 38.7 % for Eu(Ⅲ) and 20.8 % for Mn(Ⅱ), demonstrating that nFeS had a high selective adsorption for Y(Ⅲ). To understand the origins of the high selectivity of nFeS, the removal of REEs by the capping layer and the FeS-core were separately investigated. Specifically, given the hard and soft acid base principle (HASB) and the square antiprism coordination geometry of Y(Ⅲ), the adsorption of Y(Ⅲ) by the capping layer was predominantly attributed to CO and –NH2 serving as a monodentate ligand to strongly chelate with Y(Ⅲ), while Y(Ⅲ) interacted with Fe–O on the FeS-core and –COOH more via ion-exchange with Y(Ⅲ). Collectively, cooperative interactions between the capping layer and FeS-core resulted in the overall highly selective adsorption of Y(Ⅲ) by nFeS, suggest this approach has significant potential for future practical remediation and recovery applications to Y(Ⅲ) rich mining wastewaters.

Synthesis and properties of [NR4]3[SbS4] (R = Me, Et, n-Pr, n-Bu) and the crystal structures of [N(n-Bu)4]3[SbS4]⋅6H2O and [N(n-Bu)4]3[Sb(S2O3)3]·2THF

The tetra-alkylammonium tetrathioantimonate(V) salts, [NR4]3[SbS4] (R = Me, Et, n-Pr, n-Bu), have been prepared in basic solution from aqueous [NR4]OH, sulfur and Sb2S3, and characterised by microanalysis, IR, Raman, 1H and 121Sb NMR spectroscopy. The crystal structure of [N(n-Bu)4]3[SbS4]·6H2O shows the presence of the tetrahedral [SbS4]3− anion (disordered over two sites), and also connected through an H-bonding network with the lattice water molecules. The alkylammonium salts are soluble in water and, with the exception of [NMe4]3[SbS4], are also soluble in weakly polar organic solvents, including halocarbons and MeCN. Solubility increases with the R group Me < Et < n-Pr < n-Bu, making the [N(n-Bu)4)3[SbS4] a convenient reagent to explore coordination chemistry or materials applications for which water as the solvent is not suitable. [N(n-Bu)4]3[Sb(S2O3)3]·2THF, the first thiosulfate complex of a p-block element, was produced by slow decomposition of [N(n-Bu)4]3[SbS4] in THF solution in the presence of the [NH(n-Bu)3]Cl (as a source of H+), confirming the instability of the [SbS4]3− anion in acidic media, and the crystal structure of [N(n-Bu)4]3[Sb(S2O3)3]·2THF shows a trigonal antiprismatic coordination geometry with a S3O3 donor set at the antimony(III) centre in the anion.

Slow magnetic relaxation behavior of a {Dy2} complex based on a large π-conjugated bridging ligand

Binuclear lanthanide single molecule magnets (Ln-SMMs) based on large π-conjugated bridging ligands have shown potential in achieving excellent SMM performance. However, their members are still scarce until now. In this work, a novel binuclear Ln-SMM featuring a large π-conjugated bridging ligand, [Dy2(hfac)6(tpphz)]·CH2Cl2 (1), has been prepared. Its two DyIII centers are chelated and bridged by the large π-conjugated tetrapyrido[3,2-a:2′,3′-c:3′′,2′′-h:2′′′,3′′′-j]phenazine (tpphz) ligand. Three 1,1,1,5,5,5-hexafluoroacetylacetonate (hfac-) ions acting as terminal ligands further complete the square antiprism coordination geometry of each DyIII center. Magnetic measurements revealed that 1 exhibits zero field SMM behavior with a single magnetic relaxation process. The effective energy barrier (Ueff) is 13.79 K. Interestingly, dual relaxation behavior including well-separated slow relaxation (SR) and fast relaxation (FR) processes was further observed when a dc field was applied. It could be ascribed to the different single ion anisotropy of the DyIII centers, as well as a possible contribution of magnetic interactions in the system of 1. The Ueff values for the SR and FR processes are 27.3 and 1.30 K, respectively.

Structure and spectral properties of cationic lanthanide(III) complexes with carbacylamidophosphate (CAPh) ligand and tetraphenylborate-ion as counterion

New cationic lanthanide(III) complexes with carbacylamidophosphate ligand of general formula [Ln(L)2(bipy)2]BPh4 (where Ln = Eu, Tb; L- = bis(N,N'-diethylamido)(N-trichloroacetyl)triamidophosphate-ion; bipy = 2,2′–bipyridine) were synthesized and characterized by means of elemental, X-Ray and thermal analyses, IR and luminescence spectroscopy. According to the X-ray diffraction analysis the both lanthanide complexes are isostructural with octacoordinated lanthanide ions in a square antiprismatic coordination environment. It was shown that [Eu(L)2(bipy)2]BPh4 and [Tb(L)2(bipy)2]BPh4 compounds display intense red and green photoluminescence respectively with decay times over millisecond.

Facile transmetallation of [SbIII(DOTA)]- renders it unsuitable for medical applications.

The antimony(iii) complex of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate (DOTA) has been prepared and its exceptionally low stability observed. The Sb(iii) ion in Na[Sb(DOTA)]·4H2O shows an approximately square antiprismatic coordination geometry that is close to superimposable to the Bi(iii) geometry in [Bi(DOTA)]− in two phases containing this anion, Na[Bi(DOTA)]·4H2O, [H3O][Bi(DOTA)]·H2O for which structures are also described. Interestingly, DOTA itself in [(H6DOTA)]Cl2·4H2O·DMSO shows the same orientation of the N4O4 metal binding cavity reflecting the limited flexibility of DOTA in an octadentate coordination mode. In 8-coordinate complexes it can however accommodate M(iii) ions with rion spanning a relatively wide range from 87 pm (Sc(iii)) to 117 pm (Bi(iii)). The larger Bi3+ ion appears to be the best metal–ligand size match since [Bi(DOTA)]− is associated with greater complex stability. In the solution state, [Sb(DOTA)]− is extremely susceptible to transmetallation by trivalent ions (Sc(iii), Y(iii), Bi(iii)) and, significantly, even by biologically important divalent metal ions (Mg(ii), Ca(ii), Zn(ii)). In all cases just one equivalent is enough to displace most of the Sb(iii). [Sb(DOTA)]− is resistant to hydrolysis; however, since biologically more abundant metal ions easily substitute the antimony, DOTA complexes will not be suitable for deployment for the delivery of the, so far unexploited, theranostic isotope pair 119Sb and 117Sb.

Cerium(IV) fluoride complexes in solutions

The first complexes of Ce(IV)fluoride in solution have been observed and studied by 19F{1H}, 1H NMR and IR spectroscopy in saturated solutions of CeF4*H2O in Me2SO diluted by CH3CN or CH2Cl2. On the base of analysis of the temperature dependence of the 19F{1H} NMR spectra and the assumption that the usual for the solid Ce(IV) fluorocomplexes square antiprism coordination polyhedron is retained in the solution, the conclusion has been made that dynamic equilibrium between the molecular adduct [CeF4(Me2SO)4] and ionic forms [CeF3(Me2SO)5]+ and [CeF5(Me2SO)3]− exists in solution, including geometric isomers. The statistical probability of formation of [CeF4(Me2SO)4] and [CeF5(Me2SO)3]− stereoisomers has been calculated. Quantum chemical calculations of the structures of some visually distinguishable isomers of [CeFn(Me2SO)8-n]4-n (n=3–5) and [CeF4(Me2SO)3(H2O)] showed their thermodynamic stability. The experimental IR spectrum of the solution is in a good agreement with calculated spectra of [CeFn(Me2SO)8-n]4-n and [CeF4(Me2SO)3(H2O)] stable complexes.

Electronic Structure of Ytterbium(III) Solvates-a Combined Spectroscopic and Theoretical Study.

The wide range of optical and magnetic properties of lanthanide(III) ions is associated with their intricate electronic structures which, in contrast to lighter elements, is characterized by strong relativistic effects and spin-orbit coupling. Nevertheless, computational methods are now capable of describing the ladder of electronic energy levels of the simpler trivalent lanthanide ions, as well as the lowest energy term of most of the series. The electronic energy levels result from electron configurations that are first split by spin-orbit coupling into groups of energy levels denoted by the corresponding Russell-Saunders terms. Each of these groups are then split by the ligand field into the actual electronic energy levels known as microstates or sometimes mJ levels. The ligand-field splitting directly informs on the coordination geometry and is a valuable tool for determining the structure and thus correlating the structure and properties of metal complexes in solution. The issue with lanthanide complexes is that the determination of complex structures from ligand-field splitting remains a very challenging task. In this paper, the optical spectra-absorption, luminescence excitation, and luminescence emission-of ytterbium(III) solvates were recorded in water, methanol, dimethyl sulfoxide (DMSO), and N,N-dimethylformamide (DMF). The electronic energy levels, that is, the microstates, were resolved experimentally. Subsequently, density functional theory calculations were used to model the structures of the solvates, and ab initio relativistic complete active space self-consistent field calculations (CASSCF) were employed to obtain the microstates of the possible structures of each solvate. By comparing the experimental and theoretical data, it was possible to determine both the coordination number and solution structure of each solvate. In water, methanol, and N,N-dimethylformamide, the solvates were found to be eight-coordinated and have a square antiprismatic coordination geometry. In DMSO, the speciation was found to be more complicated. The robust methodology developed for comparing experimental spectra and computational results allows the solution structures of homoleptic lanthanide complexes to be determined.

Excited State Properties of Lanthanide(III) Complexes with a Nonadentate Bispidine Ligand.

EuIII, TbIII, GdIII and YbIII complexes of the nonadentate bispidine derivative L2 (bispidine=3,7‐diazabicyclo[3.3.1]nonane) were successfully synthesized and their emission properties studied. The X‐ray crystallography reveals full encapsulation by the nonadentate ligand L2 that enforces to all LnIII cations a common highly symmetrical capped square antiprismatic (CSAPR) coordination geometry (pseudo C4v symmetry). The well‐resolved identical emission spectra in solid state and in solution confirm equal structures in both media. As therefore expected, this results in long‐lived excited states and high emission quantum yields ([EuIIIL2]+, H2O, 298 K, τ=1.51 ms, ϕ=0.35; [TbIIIL2]+, H2O, 298 K, τ=1.95 ms, ϕ=0.68). Together with the very high kinetic and thermodynamic stabilities, these complexes are a possible basis for interesting biological probes.

Synthesis, Characterization, Crystal Structures, and Biological Activity of Nickel(II), Manganese(II) and Cadmium(II) Complexes Derived from 4-Bromo-N'-(1-(Pyridin-2-YL)ethylidene)benzohydrazide

Three nickel(II), manganese(II) and cadmium(II) complexes, [NiL2] (I), [MnL2] (II) and [Cd(HL)2(NO3)]·NO3 (III), derived from 4-bromo-N'-(1-(pyridin-2-yl)ethylidene)benzohydrazide (HL) were prepared and characterized by IR and UV spectra. Structures of the complexes were further confirmed by single crystal X-ray diffraction techniques (CIF files CCDC nos. 1874307 (I), 1874308 (II), and 1874309 (III)). The Ni atom in complex I and the Mn atom in complex II are in octahedral coordination. The Cd atom in complex III is in square antiprism coordination. The nickel complex is effective on the inhibition of Jack bean urease.

Regulating the distortion degree of the square antiprism coordination geometry in Dy–Na single ion magnets

A DyNa complex (1) and a DyNa2 1D chain (2) have been obtained; their square antiprism coordination geometries were changed from the bicapped triangular prism of the reported DyNa2 complex. Compounds 1 and 2 exhibit single ion magnet behavior.

A Molecular Crystal Shows Multiple Correlated Magnetic and Ferroelectric Switchings

Simultaneous control of the magnetic and electric properties of materials is crucial for their application in next-generation memory and sensor devices. Herein, we report a single-crystal Co(II) co...

Minerals As Electrode Materials for Ca-Based Rechargeable Batteries: Evaluation of the Pyroxene, Garnet, Melilite and Double Carbonate Groups

Rechargeable lithium-ion batteries dominate the consumer electronics and electric vehicle markets. However, concerns on Li availability have prompted the development of alternative high energy density electrochemical energy storage systems. Rechargeable batteries based on a Ca metal anode can exhibit advantages in terms of energy density, safety and cost. The development of rechargeable Ca metal batteries requires the identification of suitable high specific energy cathode materials. This work focuses on Ca-bearing minerals because they represent stable and abundant compounds. Suitable minerals should contain a transition metal able of being reversibly reduced and oxidized, which points to several major classes of silicates and carbonates. A recent work [1] discusses their electrode characteristics based on crystal chemistry analysis and density functional theory (DFT) calculations. The results indicate that upon Ca deintercalation, compounds such as pyroxene, garnet and double carbonate minerals could display high theoretical energy densities (ranging from 780 to 1500 Wh/kg) with moderate structural modifications. As a downside, DFT calculations indicate a hampered Ca mobility in their crystal structures with energy barriers for Ca migration exceeding 2 eV. More recent investigations found a lower energy barrier of 1 eV in the group of melilite with formula Ca2MSi2O7, where Ca ions are in a square antiprism coordination polyhedron and M is a transition metal ion in tetrahedral coordination.Acknowledgements: Authors are grateful for financial support from European Union H2020-FETOPEN funded project CARBAT-766617.[1] Torres, Luque, Tortajada, Arroyo-de Dompablo, Scientific Reports 9, 9644 (2019).

Perrhenate and Pertechnetate Complexes of U(IV), Np(IV), and Pu(IV) with Dimethyl Sulfoxide as an O-Donor Ligand.

A series of new dimethyl-sulfoxide-containing pertechnetates and perrhenates of tetravalent U, Np, and Pu were synthesized and structurally characterized by the X-ray diffractometry. In all the synthesized compounds, the actinide atoms were coordinated by eight DMSO molecules with or without an extra XO4- anion in the coordination sphere. This resulted in the square antiprismatic or capped square antiprismatic coordination of An atoms. Three or four XO4- anions play the role of outer-sphere anions. The electron and IR spectra of the compounds correlated with their crystal structure.

Supramolecular structures, thermal decomposition mechanism and heat capacity of the novel binuclear Tb(III) and Dy(III) complexes with 2,3-dimethoxybenzoic acid and 5,5′-dimety-2,2′-bipyridine

Two novel binuclear lanthanide complexes [Tb(2,3-DMOBA)3(5,5′-DM-2,2′-bipy)]2·C2H5OH (1) and [Dy(2,3-DMOBA)3(5,5′-DM-2,2′-bipy)]2·C2H5OH (2) (2,3-DMOBA = 2,3-dimethoxybenzoate, 5,5′-DM-2,2′-bipy = 5,5′-dimety-2,2′-bipyridine) have been successfully synthesized and structurally validated by single-crystal diffraction. The results of single-crystal analyses indicate the complexes contains one free ethanol molecule, and each center Ln(III) is nine-coordinated, exhibiting a distorted monocapped square anti-prismatic coordination geometry. The two center Ln(III) are bound by four 2,3-DMOBA ligands, two of which are bridging bidentate and the other two are bridging–chelating. The adjacent binuclear complexes can form 1D supramolecular structure by a pair of alternating identical C–H···O hydrogen bonding interactions, which further form 2D sheet structures. The thermal behavior of these complexes is investigated by TG-DSC/FTIR. What is more, the heat capacities of the complexes 1–2 are measured by DSC at 259.15–346.15 K, and the result indicates that the heat capacity values of the complexes gradually increased with the increase in temperature. In addition, the thermodynamic functions values (HT − H298.15K) and (ST − S298.15K) of the complexes 1–2 are calculated according to the fitted polynomial equations and the thermodynamic equation. The luminescence property of complex 1 is studied.