Triangular Dodecahedron Research Articles

Synthesis, Crystal Structure, Fluorescence and Theoretical Calculations of Three Zn(II)/Cd(II) Complexes with Bis-dentate N,N-Quinoline Schiff Base.

Three d10 metal complexes, ZnL(OAc)2 (1), CdL(OAc)2 (2) and [CdL2(NO3)2]·CH3CN (3) were synthesized using the ligand (E)-N-(3-methoxy-4-methylphenyl)-1-(quinolin-2-yl)methanimine (L) and characterized by FT-IR spectra, NMR spectra, and CHN elemental analysis. Single-crystal X-ray diffraction analysis revealed that complexes 1 and 2 are isostructural, with the central metal adopting a hexacoordinate octahedral geometry, while complex 3 adopts a triangular dodecahedron geometry. Thermal gravimetric analysis showed that these complexes exhibit good thermal stability. Solid-state fluorescence spectroscopy measurements demonstrated that complexes 1-3 exhibit bright yellow-green fluorescence (λem = 564nm for 1; 524nm for 2; 542nm for 3), suggesting their potential as photoluminescent materials. Furthermore, DFT calculations, including frontier molecular orbitals, energy levels, and surface electrostatic potential, provided insights into the structural and electronic spectral properties of complexes 1-3.

Structural, spectral, and thermal gravimetric studies of lanthanum complexes with N,N'-tetraethyl-N''-(trichloroacetyl)phosphortriamide, 2,2'-bipyridine, and nitrate anion

Coordination compounds of lanthanum with carbacylamidophosphate – N,N'-tetraethyl-N''-(trichloroacetyl)phosphortriamide (HL) and 2,2'-bipyridine (bipy) of composition LaLbipy2(NO3)2 and LaL3bipy were synthesized and studied by means of X-ray, thermal gravimetric analyses, IR, and NMR spectroscopy. It was established that all the ligands in the complexes are coordinated towards lanthanum in bidentate manner. Coordination number of central ion equals ten and eight for LaLbipy2(NO3)2 and LaL3bipy, respectively. Coordination polyhedron of LaIII ion has distorted geometry between bicapped square antiprism and sphenocorona in LaLbipy2(NO3)2 and between square antiprism and triangular dodecahedron in LaL3bipy. The bonds lengths La–O and La–N are commensurate in the synthesized complexes. The both structures are characterized by the presence of numerous intermolecular interactions, which have been analyzed using Hirshfeld surface tool. A feature of the complex LaLbipy2(NO3)2 is the presence of two crystallographically independent molecules in crystal. The compounds LaLbipy2(NO3)2 and LaL3bipy are thermally stable to 1750С and 1650С, respectively. A feature of the tris-complex LaL3bipy is the presence of a phase transition at a temperature of 960С.

Crystal structure of tetra-phenyl phosphate tetra-kis-[dimethyl (2,2,2-tri-chloro-acet-yl)phos-pho-ramidato]lutetium(III), PPh4[LuL4

A lutetium(III) complex based on the anion of the ligand dimethyl (2,2,2-tri-chloro-acet-yl)phospho-ramidate (HL) and tetra-phenylphosphonium, of composition PPh4[LuL 4] (L = CAPh = carbacyl-amido-phosphate), or (C24H20)[Lu(C4H6Cl3NO4P)4], has been synthesized and structurally characterized. The X-ray diffraction study of the compound revealed that the lutetium ion is surrounded by four bis-chelating CAPh ligands, forming the complex anion [LuL 4]- with a coordination number of 8[O] for LuIII, while PPh4 + serves as a counter-ion. The coordination geometry around the Lu3+ ion was determined to be a nearly perfect triangular dodeca-hedron. The complex crystallizes in the monoclinic crystal system, space group P21/c, with four mol-ecules in the unit cell. Weak hydrogen bonds O⋯HC(Ph), Cl⋯HC(Ph) and N⋯HC(Ph) are formed between the cations and anions. For a comparative study, HL-based structures were retrieved from the Cambridge Structural Database (CSD) and their geometries and conformations are discussed. A Hirshfeld surface analysis was also performed.

Lanthanoid(Ⅲ) complexes containing bipyridinedicarboxylic acid ligand: Synthesis, spectroscopic characterization, thermal analysis, and crystal structures

The present report deals with the synthesis of the two complexes of respective formula {[Ce(bpydcb)(HCOO)(H2O)]·H2O}n (1) and [Eu2(bpydcb)3(H2O)2(DMF)]·3H2O·0.5DMF (2) the structure of both of them elucidated by single-crystal X-ray diffraction and powder X-ray diffraction to demonstrated that complexes 1 and 2 crystallize in a similar space group P21/c as a monoclinic system with high crystal purity. X-ray Single crystal diffraction analysis demonstrates, nine-coordinate environment of Ce (Ⅲ) in the complex 1 and octa-coordinate environment of Eu (Ⅲ) in the complex 2. And discovered the tricapped trigonal prism of cerium complex and the triangular dodecahedron of europium complex. Meanwhile, the complexes were characterized by elemental, infrared, ultraviolet, fluorescence and thermal analysis. Fluorescence testing shows that complex 1 emits ligand fluorescence, while complex 2 emits fluorescence from the ligand to the central ion, emitting characteristic fluorescence of europium ion, both complexes can emit strong fluorescence. The thermogravimetric analysis results show that the thermal stability of complex 1 is better than that of complex 2, and its organic framework only begins to collapse after 375 ℃.

Photophysical properties of tris(benzoyltrifluoroacetonate)Eu(III) with pyrazole complex and its precursor

The precursor, [Eu(btfa)3(H2O)2] with yield of 84 % and its complex with monodentate pyrazole, [Eu(btfa)3(pz)2] were isolated successfully. To the best of our knowledge, no previous reports of such synthesis with a high yield of [Eu(btfa)3(H2O)2] exist in literature. Single crystal X-ray diffraction (SC-XRD) analysis demonstrates, octa-coordinate environment of Eu (III) in both the complexes. The geometry of these complexes was obtained from SHAPE v2.1 and found triangular dodecahedron (D2d) and square antiprism (D4d) for [Eu(btfa)3(H2O)2] and [Eu(btfa)3(pz)2], respectively. These complexes were further characterized by elemental, thermal analysis (TGA/DTA) and ATR-IR spectroscopy. The lifetime of [Eu(btfa)3(pz)2] (546 ± 0.35 μs) is much longer than that of its precursor [Eu(btfa)3(H2O)] (335 ± 0.11 μs). The overall quantum yield of [Eu(btfa)3(pz)2] complex (21 %) is seven times larger than its precursor (3 %). The Judd-Ofelt intensity parameters accredit that [Eu(btfa)3(pz)2] is more polarizable (Ω2 = 33.56 × 10-20 cm2) than its precursor, [Eu(btfa)3(H2O)2] (Ω2 = 13.95 × 10-20 cm2).

Crystal structure of a layered phosphate molybdate K2Gd(PO4)(MoO4)

The title compound dipotassium gadolinium(III) phosphate(V) molybdate(VI), K2Gd(PO4)(MoO4), was synthesized from a high-temperature melt starting from GdF3 as a source of gadolinium. Its structure is isotypic with other M I 2 M III(M VIO4)(PO4) compounds, where M I = Na, K or Cs, and M III = rare-earth cation, M VI = Mo or W. The three-dimensional framework is built up from [Gd(PO4)(MoO4)] anionic sheets, which are organized by adhesion of [GdPO4] layers and [MoO4] tetrahedra stacked above and below these layers. The interstitial space is occupied by K cations having eightfold oxygen coordination. The polyhedron of GdO8 was estimated to be a triangular dodecahedron by the continuous shape measurement method.

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.

Effect of coordinated anions on ferromagnetically coupled Dy2 zero-field single-molecule magnets.

A new hydrazone Schiff base ligand was condensed from 2-hydroxy-3-methoxybenzaldehyde and pyrimidine-4-carbohydrazide {H2L = (E)-N'-(2-hydroxy-3-methoxybenzylidene)pyrimidine-4-carbohydrazide}, which was used to assemble two new Dy2 complexes Dy2L2(DMF)2(NO3)2 (1) and Dy2L2(DMF)2(AcO)2 (2). Notably, the coordinated anions have a subtle effect on the coordination configurations of the Dy3+ ions and the magnetic properties of the two Dy2 complexes. The Dy3+ ions in 1 and 2 have the same N2O5 coordination environment but show the triangular dodecahedron and the biaugmented trigonal prism coordination configurations, respectively. Magnetic measurements revealed that both 1 and 2 have intramolecular ferromagnetic interactions between the Dy3+ ions and show single-molecule magnet behaviors at 0 Oe, with Ueff/k values of 58.2 K for 1 and 59.9 K for 2. These magnetic properties may be explained by theoretical calculations.

1D-photosensitized lanthanide polymers with flexible 4, 4′-bipyridyl linker

Three new ternary lanthanide complexes, [Ln(fod)3(4,4′-bpy)]n (Ln = Nd, Sm and Tb) were synthesized using asymmetric fluorinated β-diketone, 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione, as first sensitizer and 4, 4′-bipyridyl, the linker. The structural characterizations were carried out through various techniques viz., 1H NMR, FT-IR, single crystal X-ray diffraction (SC-XRD) and thermal analysis. Single crystal X-ray diffraction (SC-XRD) analysis demonstrates a 1D-polymeric chain structure of [Nd(fod)3(4,4′-bpy)]n in which Nd (III) ions are octa-coordinate with distorted square antiprismatic geometry. The structure of samarium and terbium complexes were optimized by the sparkle PM7 model using MOPAC implemented in LUMPAC and found to be distorted triangular dodecahedron The thermal studies shows that the complexes are thermally stable and acquire volatility without decomposition. The 1H NMR of these complexes are similar. The protons of 4, 4ʹ-bpy are largely shifted upfield in the Tb complex followed by Nd and Sm. The detailed photoluminescence and decay curves of these polymeric complexes have been discussed in solution and solid state. The emission spectra obtained for all the complexes display their characteristic emission peaks. The terbium complex shows pure green luminescence and exhibits a longer lifetime of 406 µs. The [Sm(fod)3(4,4′-bpy)]n displays color tuning during interphase and also with a change in excitation wavelength from turquoise to pure yellow via green. All the synthesized complexes exhibiting remarkable photophysical properties ensures their importance in various fields.

Structure, slow magnetic relaxation behavior and bacteriostatic activity of a novel Dy4 cluster

A novel tetranuclear Dy(III)-based cluster, namely [Dy4(CO3)L4 (acac)2(CH3OH)2(CH2OH)2]·2CH3OH (1) (where H2L is 2-(hydroxyimino)-2-[(5-bromo-2-hydroxyphenyl)methylene]hydrazide and Hacacis acetylacetonate) has been constructed by employing a newly prepared Schiff based ligand H2L. X-ray diffraction data reveal that 1 is mainly consist of a rhombic Dy4core, in which the four Dy3+ ions are bridged by six μ-O atoms from four ligands H2L and two μ2-O atoms from thein situformed CO32−via spontaneous fixation of atmospheric CO2.The crystalstructure of 1 possesses two distinct Dy3+ ions coordinationcenter, and the nine-coordinated Dy73+ionscenter presenting a distorted spherical capped square antiprism geometry and eight-coordinated Dy43+ionscenter presenting a distorted triangular dodecahedron geometry.Magnetic study indicates that 1displays slow magnetic relaxation behavior under Hdc = 0 Oe filed. Furthermore, the fluorescence property investigation reveals that 1shows DyIIIcharacteristic emission peaks. Moreover, theantibacterial activity and mechanism of 1 have been systemically studied, and cluster 1 possesses well antibacterial activity on five common bacteria (Escherichia coli, Staphylococcus aureus, Staphylococcus albus, Bacillus subtilis, and Micrococcus luteus). Inaddition,the interaction between 1 and DNA have been studied.

Lanthanide dimers in coordination chains constructed by sole dicarboxylate ligand for single-molecule magnet behavior and magnetocaloric effect

The solvothermal reaction of Dy(III) and Gd(III) ions with 2,5-di‑hydroxy-benzene-1,4-di-carboxylic acid (H4dhbdc) produced two new isostructural lanthanide(III) coordination chains with the general formula {[Ln2(H2dhbdc)3(H2O)8]·6H2O}n [Ln = Dy (1) and Gd (2)]. The chains consist of carboxylate-bridged dilanthanide(III) units linked by H2dhbdc2− ligands in an end-to-end bridging mode. The Dy3+ and Gd3+ ions are located in slightly distorted biaugmented trigonal prism (C2v) and triangular dodecahedron (D2d) coordination environments, respectively. Magnetic studies reveal the extremely weak antiferromagnetic interaction (J = -0.041 cm−1) between the magnetically isotropic GdIII ions in 2. The dysprosium analogue was found to exhibit single-molecule magnet (SMM) behavior with a prominent QTM effect under zero dc field, which is largely due to large single-ion magnetic anisotropy of individual Dy3+ ions and weak antiferromagnetic interaction. For the gadolinium chain, the magnetocaloric effect (MCE) was observed with a magnetic entropy change of 20.2 J kg−1 K − 1. These results demonstrate a dicarboxylate synthetic route for the preparation of coordination polymers containing dilanthanide units for SMM and MCE applications.

Self-Assembly of Triple-Stranded Lanthanide Molecular Quasi-Lantern Containing 2,2'-Bipyridine Receptor: Luminescence Sensing and Magnetic Property.

Ln2L3-type supramolecular architectures have received significant attention recently due to their unique magnetism and optical properties. Herein, we report the triple-stranded Ln2L3-type lanthanide molecular quasi-lanterns, which are fabricated by the deprotonation self-assembly of a linear ligand featuring a β-diketone chelating claw and 2,2'-bipyridine (bpy) moiety with lanthanide ions (Ln = Eu3+ and Dy3+). The crystal structure analysis indicates that Eu3+ and Dy3+ ions are all coordinated by eight oxygen donors but in different coordination geometries. The eight oxygen donors in Eu2L3 and Dy2L3 are arranged in a square antiprism and triangular dodecahedron geometry, respectively. Taking into account the fact that the bpy moiety has a strong coordination affinity for transition metal ions, luminescence sensing toward Cu2+ ions has been demonstrated with Eu2L3, bearing a detection of limit as low as 2.84 ppb. The luminescence sensing behavior of Eu2L3 is ascribed to the formation host-guest complex between Eu2L3 and Cu2+ ions with a 1:2 binding ratio. Dynamic AC susceptibility measurements for Dy2L3 reveal the relaxation of magnetization in it. This work provides a potential way for design and fabrication of lanthanide-based molecular materials with functions endowed by the ligands.

Significant Control on Zero-field Quantum Tunneling of Magnetization in Dysprosium Based Single-Molecule Magnets via Orientation of the Anilato Ligand.

Tuning the bridging fashion of anilato ligand in dinuclear DyIII complexes, reveals a sizable effect on the slow relaxation of magnetization. Combined experimental and theoretical studies divulge that the geometry with high order axial symmetry (pseudo square antiprism) reduces the transverse crystal fields corresponding to QTM resulting in a significant increase in energy barrier (Ueff = 518 cm-1) through the Orbach relaxation process whereas the geometry with lower symmetry (triangular dodecahedron, pseudo D2d) enhances the transverse crystal fields that accelerate the ground state QTM process. Notably, the value 518 cm-1 represents the highest energy barrier among anilato ligand based SMMs.

Synthesis, crystal structure, and sensing properties of organic molecules based on a Terbium-nitronyl nitroxide complex

A new Terbium-nitronyl nitroxide radical complex [Tb(hfac)3(NITPh-m-CHO)2]·0.5C7H16 (Tb-rad) (hfac = hexafluoroacetylacetonate; NITPh-m-CHO = 2-(3′-formylphenyl)-4,4,5,5-tetramethylimidazoline-l-oxyl-3-oxide) was prepared and characterized. Tb-rad crystallizes in triclinic space group P1¯, possessing a mononuclear structure, in which the geometrical configuration of Tb(III) is triangular dodecahedron consisted of six oxygen atoms from three hfac ligands and two oxygen atoms from the NO groups of two NITPh-m-CHO ligands. In Tb-rad, isolated mononuclear structures were connected to form 1D supramolecular chain structures via intermolecular π···π interaction and free n-heptane molecules fill the void in the crystal. Significantly, the luminescence explorations demonstrate that Tb-rad is an excellent fluorescent sensor for identifying nitrobenzene (NB) and nitromethane (NM) molecules. Because of the linear relationship at low concentration with the quenching constant (Ksv) is 5.4 × 105 and 6.6 × 103 M−1 for NB and NM, respectively, it can be considered as a potential luminescent sensor for detecting NB and NM molecules. Moreover, the possible sensing mechanisms of selective detection have been discussed in detail.

Mononuclear Lanthanide Complexes in Triangular Dodecahedron Geometry: Manifestation of Single Ion Magnet Behavior for DyIII Analogue

In this work, a tridentate N,N,O ligand [(E)-4-nitro-2-((pyridine-2-ylmethylene)amino)phenol] (LNO2H) is employed for the synthesis of neutral structurally similar complexes [DyIII(LNO2)2(Cl)(H2O)]•H2O (1) and [ErIII(LNO2)2(Cl)(CH3OH)]•3CH3OH (2). Both complexes are characterized by single-crystal X-ray diffraction studies. LnIII ion in complexes 1 and 2 is eight coordinated and possesses triangular dodecahedron geometry as confirmed by the SHAPE analysis. The Hirshfeld surface calculation emphasizes the importance of hydrogen bond interaction that controls the overall crystal packing. The magnetic studies reveal that complex 1 shows single ion magnet (SIM) behavior with an effective energy barrier of 34.16 K and pre-exponential parameter 6.51 × 10–6 s. The CASSCF based ab initio calculations were performed on complexes 1 and 2 to extract SH parameters and the plausible magnetic relaxation dynamics.

Pure red-light emitting europium based complexes as efficient UV light converters: synthesis, crystal structure and photoluminescence properties.

This paper reports three new crystallographically characterized europium complexes with composition as follows: [Eu(fod)3(L1)] (1), [Eu(fod)3(L2)] (2) and [Eu(fod)3(L3)] (3) {L1 = benzimidazole (bzi), L2 = 4,7-diphenyl-1,10-phenanthroline (bath), L3 = 2-(2-pyridyl) benzimidazole (py-im) and fod = anion of 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione (Hfod)}. The single crystal (SC) XRD analysis shows that complex 1 is seven-coordinated while complexes 2 and 3 are eight-coordinated with the geometrical structures of a mono-capped octahedron and a trigonal dodecahedron, respectively. The NMR spectra of the complexes validate the SC-XRD results in solution. The complexes are stable in solution as no dissociation of any ligand was observed in the NMR spectra of the complexes. The photophysical properties of the complexes in solution, solid state, and PMMA thin films were studied. The hypersensitive transition 5D0 → 7F2 dominates the emission spectra in all phases, showing the highly asymmetric environment around the Eu(III) ion. The bath ligand is found to be the best sensitizer of the Eu ion and hence complex 2 shows the strongest luminescence properties with the highest absolute quantum yield among the three complexes. The CIE coordinate analysis shows that pure red-luminescence is emitted by the Eu complexes in the solid state since the coordinates found in this phase are closer to the standard NTSC 1987 values. The optical band gaps were determined for the complexes and the observed values suggest that the complexes can have possible applications in the field of semiconductor materials.

Slow magnetic relaxation of a mononuclear dysprosium complex derived from 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione and 1,10-phenanthroline

A mononuclear dysprosium complex with a triangular dodecahedron geometry behaves as a single-molecule magnet with the effective barrier Ueff = 193 K.

Assembly of tetra-nuclear lanthanide compounds: Structures, magnetic refrigeration and slow relaxation of magnetization

Two novel tetranuclear lanthanide compounds with the formula [Ln4(L1)2(L2)2(μ2- OCH3)2(CH3OH)2]·CH3OH (Ln = Gd (1), Dy (2), H2L1 = 2-[(2-(hydroxyimino)propanehydrazide)methyl]-8-hydroxyquinoline, H3L2 = 2-[(2-(N'-acetylhydrazino)propanehydrazide)methyl]-8-hydroxyquinoline) were successfully prepared, and structurally and magnetically characterized. Crystal structural analyses reveal that two compounds are isostructural and they all consist of a tetranuclear Ln4 cluster. All Ln(III) ions in them are eight-coordinated and located in a distorted triangular dodecahedron geometry. Magnetic studies indicate that 1 exhibits large magnetocaloric effect with the entropy change (-ΔSm) of 32.10 J Kg−1 K−1 (at T = 2.0 K and ΔH = 7 T), and 2 displays slow magnetic relaxation behaviors.

Preparation, crystal structure, and luminescent properties of CAPh containing lanthanide(III) complexes with various amounts of coordinated solvent molecules

A series of mixed–ligand lanthanide complexes, Ln(Pip)3( iPrOH) x (x = 2 for Ln(III) = La, Ce–Nd, Sm–Eu and x = 1 for Ln(III) = Gd–Lu; HPip is 2,2,2-trichloro-N-(dipiperidin-1-yl-phosphoryl)acetamide, the carbacylamidophosphate (CAPh) ligand), has been synthesized and identified. Using indirect techniques (FT-IR, 1H, 31P-NMR, and absorption spectroscopy) and the X-ray diffraction method (for europium complex) it was found that three Pip -ligands are coordinated to lanthanide(III) ions in a bidentate chelate manner via oxygen atoms of the carbonyl and phosphoryl groups. The oxygen atoms of 2-propanol molecules complete the coordination number of Ln(III) ions to eight (for Ln from La to Eu) or seven (for Ln from Gd to Lu). The europium complex Eu(Pip)3( iPrOH)2 crystallizes in the Рī space group. The {EuO8} polyhedron has a triangular dodecahedron (TDD-8) conformation and exists in a form of a t1t2p2+MC isomer. The luminescent properties of Eu(Pip)3( iPrOH)2 polycrystalline samples were investigated at 300, 77, and 4.2 K.

Halogen Bond Mediated Self-Assembly of Mononuclear Lanthanide Complexes: Perception of Supramolecular Interactions, Slow Magnetic Relaxation, and Photoluminescence Properties.

Five new mononuclear lanthanide complexes, [LnL2][Et3NH]·THF/H2O (Ln = Nd, Tb, Dy) (H2LCl = 2-bis(2-hydroxy-3,5-dichloro benzyl)aminomethyl]pyridine), Ln = Nd (1), Tb (2), and Dy (3), and (H2LBr = 2-bis(2-hydroxy-3,5-dibromo benzyl)aminomethyl]pyridine), Ln = Nd (4, H2O) and Tb (5), were synthesized and structurally characterized by single-crystal X-ray diffraction analyses. Being isostructural in all the five cases, the metal center is octa-coordinated with a triangular dodecahedron (D2d symmetry) geometry, and it is independent of the halogen substitution (Cl/Br). This close similarity is due to the composite interplay of hydrogen/halogen bond interactions that control the overall crystal packing, yet notable differences in association patterns among the individual ones arise from the subtle stereo-electronic requirement of individual molecules in the three-dimensional (3D) architecture. Hirshfeld surface and density functional theory (DFT) calculations clearly vouch for the importance of the hydrogen bond and halogen bond interactions observed in the structure. Detailed magnetic measurements using direct-current and alternating-current susceptibility measurements show slow magnetic relaxation in 3, a characteristic feature of the single-molecule magnets (SMMs), which is not shown by 1 and 2. Steady-state and time-resolved photoluminescence of Tb(III) complexes shows a strong ligand-to-metal energy transfer that can be modulated by changing the substitution on phenolic ligands. The results from these analyses indicate that it may be advantageous to consider the subtle role of hydrogen bond (HB)/halogen bond (XB) intermolecular interactions judiciously for the design of SMMs and luminescent materials based on halogen-substituted ligands.