TbIII Ions Research Articles

Binuclear TbⅢ complex used for the fluorescent detection of 2, 6-pyridindicarboxylic acid, an anthrax biomarker

Anthrax is a potentially highly lethal acute infectious disease caused by the zoonotic bacterium Bacillus anthracis, which poses a threat to human life and health. 2, 6-Pyridinedicarboxylic acid (DPA) is a significant component of bacterial spores as a typical anthrax biomarker. Therefore, it is imperative to develop a simple and efficient detection method for DPA. Here, we successfully synthesized a binuclear terbium complex with formulas [Tb2(DMOMP)2(CH3OH)2(H2O)4Cl2]·2Cl·2CH3OH, which is constructed by 2, 6-dimethoxy-4-methylphenol (DMOMP) and TbⅢ ion. Each TbⅢ ion center is encapsulated by seven O atoms and one Cl− anion. Based on this, the encapsulated coordination environment facilitated efficient ligand energy transfer via the “antenna effect”. Therefore, the complex exhibits interesting luminescence response characteristics, with fast and stable green fluorescence response to DPA, low detection limit Ksv = 1.08 × 10−5 M−1, and fluorescence lifetime τ = 754.93 μs. [Tb2(DMOMP)2(CH3OH)2(H2O)4Cl2]·2Cl·2CH3OH has excellent fluorescence properties and strong immunity to interference and is capable of sensitively detecting the B. anthracis biomarker DPA, allowing it to be potentially used as an effective fluorescent probe and providing a viable strategy for effective anthrax fever prevention.

Recent Developments of Nontraditional Single-Molecule Toroics.

Single-molecule toroics (SMTs), defined as a type of molecules with toroidal arrangement of magnetic moment associated with bi-stable non-magnetic ground states, are promising candidates for high-density information storage and the development of molecule based multiferroic materials with linear magneto-electric coupling and multiferroic behavior. The design and synthesis of SMTs by arranging the magnetic anisotropy axis in a circular pattern at the molecular level have been of great interest to scientists for last two decades since the first detection of the SMT behavior in the seminal Dy3 molecules. DyIII ion has long been the ideal candidate for constructing SMTs due to its Kramer ion nature as well as high anisotropy. Nevertheless, other LnIII ions such as TbIII and HoIII ions, as well as some paramagnetic transition metal ions, have also been used to construct many nontraditional SMTs. Therefore, we review the progress in the studies of SMTs based on the nontraditional perspective, ranging from the 3D topological to 1D&2D&3D polymeric SMTs, and 3d-4f to non Dy-based SMTs. We hope the understanding we provide about nontraditional SMTs will be helpful in designing novel SMTs.

Bright LanthanideIII Triboluminescence despite Low Photoluminescence, and Dual Triboluminescence and Mechano‐Responsive Photoluminescence

AbstractIn pursuit of a new family of mechanically responsive luminescent materials, it is aimed to differentiate triboluminescence (TL) from photoluminescence (PL). A β‐diketonate ligand with tert‐butyl groups (2,2,6,6‐tetramethylheptane‐3,5‐dionate: tmh) is selected to quench EuIII‐centered PL via ligand‐to‐metal charge transfer, whereas tmh provides efficient photosensitization of TbIII ions. Bright TL is observed from the EuIII and TbIII homodinuclear complexes despite the fact that their PL quantum yields differed by a factor of >50. Nanomechanical tests reveal the ductility of the crystals, suggesting they are ideal for accumulating deformation energy before breakage. Furthermore, a TL/PL color difference is observed for a TbIII/EuIII heterodinuclear complex, and grinding results in mechanochromic luminescence (MCL); this is the first example of a dual TL‐ and MCL‐active lanthanideIII coordination compound. The photophysical properties before, during, and after grinding are investigated and correlated with powder and single‐crystal crystallographic data.

Metallogels: a novel approach for the nanostructuration of single-chain magnets.

In this study we demonstrate that single-chain magnets (SCMs) can be assembled in gel phase and transferred intact on surface. We take advantage of a family of SCMs based on TbIII ions and nitronyl-nitroxides radicals functionalized with short alkyl chains known to form crystalline supramolecular nanotubes interacting with heptane acting as crystallizing solvent. When the radicals are functionalized with long aliphatic chains a robust gel is formed with similar structural and functional properties respect to its crystalline parent. Indeed, a small-angle X-ray scattering (SAXS) study unambiguously demonstrates that the gel is made of supramolecular nanotubes: the high stability of the gel allows the determination from SAXS data of precise nanotube metrics such as diameter, helical pitch and monoclinic cell of the folded 2D crystal lattice along the tube direction. Additionally, static and dynamic magnetic investigations show the persistence of the SCM behavior in the metallogel. Last, on-surface gelation provides thick films as well as sub-monolayer deposits of supramolecular nanotubes on surface as evidenced by atomic force microscopy (AFM) observations. This paves the road toward magnetic materials and devices made of SCMs profiting of their isolation on surface as individual chains.

A lanthanide luminescent sensor for the detection of 4-nitrophenol in aqueous media.

The development of facile luminescent sensors for detecting nitrophenols in aqueous media is of great necessity for the safety of the environment and human health, as they are a class of widespread toxic organic pollutants that cause serious adverse effects upon consumption. Based on a new multidentate asymmetric ligand (H2L) in which salicylamide and 4-nitryl-salicylaldimine are spaced by 1,2-bis(2-ethoxy)ethyl, a new hydrostable lanthanide intercycle, [Tb2L2(NO3)2]·CH3CN (Tb-[2]c), was prepared to act as a new luminescent sensor for 4-NP in water media. Structural analysis indicated that two fully deprotonated L2- ligands in cis-configuration and μ2-L-κ2O1:κO2:κO4:κN2:κO5 coordination mode were interlocked by two TbIII ions to render the emitted TbIII encapsulated by L2- for lessening non-radiative transitions. The excellent sensitizing capability of the ligand L2- to TbIII was ascertained by both experimental methods and theoretical calculations. The sensing exploration indicated that Tb-[2]c exhibited highly sensitive and selective recognition of 4-NP against other nitroaromatics in aqueous media. The recognition mechanism could be attributed to the internal filtration effect (IFE) mechanism when DFT calculations and accumulating experimental evidence were combined.

Tuning Nuclearity of Biradical-Ln Functional Compounds with Single-Molecule Magnet Behavior and Near-Infrared Luminescence

Utilizing an hexadentate nitronyl nitroxide biradical bisNITbpym, two series of biradical-4f clusters, namely [Tb2(hfac)6(bisNITbpym)2]·CHCl3 (1), [Dy2(hfac)6(bisNITbpym)2] (2), and [Ln4(hfac)12(bisNITbpym)2] (LnIII = YIII3, TbIII4 and YbIII5) (bisNITbpym = 2,2′-dipyridyl-5,5′-bis(1′-oxyl-3′-oxido-4′,4′,5′,5′-tetramethyl-4,5-hydro-1H-imidazol-2-yl); hfac = hexafluoroacetylacetonate), have been smoothly obtained via regulating the ratio of LnIII metal to biradical bisNITbpym. In compounds 1 and 2, the bisNITbpym ligand links two TbIII ions to yield a dinuclear pattern. Meanwhile, 3–5 exhibit an annular tetranuclear structure with biradical bisNITbpym, enwrapping and bridging four LnIII ions. Single-molecule magnet behavior of the Dy derivate is confirmed through frequency-dependent ac signals. Furthermore, this comparative exploration of dinuclear and tetranuclear systems indicates that spatial symmetries around LnIII ions have an important impact on magnetic dynamics. Near-infrared luminescence and slow magnetic relaxation have been observed in the YbIII derivative, which can act as a promising multifunctional probe in the aspect of fluoroimmuno assays. Our present work not only successfully acquires a multifunctional YbIII-based compound but also achieves the regulation of nuclearity and magnetic property of the nitronyl nitroxide biradical-LnIII system.

Effective Photosensitization in Excited-State Equilibrium: Brilliant Luminescence of TbIII Coordination Polymers Through Ancillary Ligand Modifications.

Molecular photosensitizers provide efficient light-absorbing abilities for photo-functional materials. Herein, effective photosensitization in excited-state equilibrium is demonstrated using five TbIII coordination polymers. The coordination polymers are composed of TbIII ions (emission center), hexafluoroacetylacetonato (photosensitizer ligands), and phosphine oxide-based bridges (ancillary ligands). The two types of ligand combinations induces a rigid coordination structure via intermolecular interactions, resulting in high thermal stability (with decomposition temperatures above 300 °C). Excited-triplet-state lifetimes of photosensitizer ligands (τ=120-1320 μs) are strongly dependent on the structure of the ancillary ligands. The photosensitizer with a long excited-triplet-state lifetime (τ≥1120 μs) controls the excited state equilibrium between the photosensitizer and TbIII , allowing the construction of TbIII coordination polymer with high TbIII emission quantum yield (≥70 %).

Six-coordinated rare earth organoarsinate complexes: Crystal structure, luminescent and magnetic properties investigation

An isostructural series of rare earth complexes has been synthesized by using the dimethylarsinate ligand. All complexes have the formula [Ln(Me2AsO2)3][H2O]8 (Ln ​= ​Sm(1), Eu(2), Gd(3), Tb(4), Dy(5), Ho(6), Er(7), Tm(8), Yb(9), Y(10)). They are the first rare earth complexes ligated by organoarsinate. Crystallographic characterizations reveal that all the compounds feature 1D chain-like arrangements, in which two rare earth ions are bounded by three dimethylarsinate ligands (syn,syn, μ2-ƞ1:ƞ1) and the rare six-coordinated rare earth ions display ideal octahedron coordination geometry. The solid state photoluminescent studies reveal that compounds 2 and 4 exhibit the characteristic emission band of the EuIII and TbIII ions respectively. Magnetic measurements indicate Gd(3) shows magnetocaloric effect (MCE) with entropy change of 24.92 ​J ​kg–1 K–1 for ΔH ​= ​0 – 7 ​T at 3 ​K. The Dy(5) and Yb(9) show field induced slow relaxation, which is rare for octahedron coordinate LnIII compounds.

Stable terbium metal-organic framework with turn-on and blue-shift fluorescence sensing for acidic amino acids (L-aspartate and L-glutamine) and cations (Al3+ and Ga3+).

A terbium-based metal-organic framework, namely {[Tb2(ADIP)(H2ADIP)(HCOOH)(H2O)2]·2DMF·2H2O}n (Tb-MOF, H4ADIP = 5,5'-(anthracene-9,10-diyl) diisophthalic acid), was synthesized and characterized. The single-crystal structure analysis shows that the Tb-MOF crystallizes in the C2/C space group in the monoclinic system and its asymmetric unit contains two TbIII ions, one ADIP4-, one H2ADIP2-, one coordinating formic acid and two coordination water molecules. Tb-MOF has a three-dimensional porous structure with a porosity of 41.5%. Tb-MOF is a highly selective and sensitive fluorescence turn-on and blue-shift sensor for L-aspartate (Asp), L-glutamine (Glu), Al3+ and Ga3+with detection limits of 0.25, 0.23, 0.069 and 0.079 μM, respectively. Experimental studies and theoretical calculations show that the sensing process is mainly attributed to the energy transfer and the absorbance caused enhancement (ACE) mechanism. Therefore, Tb-MOF is a good multi-response fluorescence sensor for acidic amino acids and Al3+, Ga3+cations.

Crystalline paramagnetic supramolecular 2D-polymer of the tetra(4-pyridyl)porphyrin and terbium(III) complex.

A new promising method for the preparation of crystalline 2D polymers based on tetra(4-pyridyl)porphyrin has been developed. Radical anion {H2T(4-Py)P˙-} species are used as the starting material. A new solid-state supramolecular array [{H2T(4-Py)P}·{TbIII(TMHD)3}2]·2.84C6H14 (1) in which porphyrin units are bridged with TbIII ions to form a self-assembled 2D polymer has been obtained. The complex contains neutral porphyrin macrocycles, which is supported by optical and magnetic data. High-spin paramagnetic TbIII ions are weakly antiferromagnetically coupled in accordance with rather long distances between them.

A Chiral Lanthanide Tag for Stable and Rigid Attachment to Single Cysteine Residues in Proteins for NMR, EPR and Time-Resolved Luminescence Studies.

A lanthanide‐binding tag site‐specifically attached to a protein presents a tool to probe the protein by multiple spectroscopic techniques, including nuclear magnetic resonance, electron paramagnetic resonance and time‐resolved luminescence spectroscopy. Here a new stable chiral LnIII tag, referred to as C12, is presented for spontaneous and quantitative reaction with a cysteine residue to generate a stable thioether bond. The synthetic protocol of the tag is relatively straightforward, and the tag is stable for storage and shipping. It displays greatly enhanced reactivity towards selenocysteine, opening a route towards selective tagging of selenocysteine in proteins containing cysteine residues. Loaded with TbIII or TmIII ions, the C12 tag readily generates pseudocontact shifts (PCS) in protein NMR spectra. It produces a relatively rigid tether between lanthanide and protein, which is beneficial for interpretation of the PCSs by single magnetic susceptibility anisotropy tensors, and it is suitable for measuring distance distributions in double electron–electron resonance experiments. Upon reaction with cysteine or other thiol compounds, the TbIII complex exhibits a 100‐fold enhancement in luminescence quantum yield, affording a highly sensitive turn‐on luminescence probe for time‐resolved FRET assays and enzyme reaction monitoring.

Efficient Sensitized Luminescence of Binuclear Ln(III) Complexes Based on a Chelating Bis-Carbacylamidophosphate.

Binuclear rare earth complexes Ln2L3phen2 (LnIII = NdIII, SmIII, EuIII, TbIII, DyIII, YbIII and YIII) with bis-CAPh type ligand - tetramethyl N,N'-(2,2,3,3,4,4-hexafluoro-1,5-dioxopentane-1,5-diyl)bis(phosphoramidate) (H2L) and 1,10-phenanthroline (phen) were synthesized and characterized by elemental analysis, IR, NMR, absorption and luminescence spectroscopy. Luminescence measurements were performed for all the complexes in solid state and for the EuIII, TbIII and YIII complexes - in solution in DMSO as well. The effective energy transfer from organic ligands to LnIII ions strongly sensitizes the LnIII ions emission and under excitation by UV light, the complexes exhibited bright characteristic emission of lanthanide metal centers. It was found that the energy level of the ligands lowest triplet state in the complexes matches better to resonance level of EuIII rather than TbIII ion. Depending on temperature the emission decay times of solid europium and terbium complexes were in the range of 1.5-2.0ms. In solid state at room temperature the EuIII complex possess intense luminescence with very high intrinsic quantum yield 91% and decay time equal 1.88ms.

Europium(III), Terbium(III), and Gadolinium(III) Oxamato-Based Coordination Polymers: Visible Luminescence and Slow Magnetic Relaxation.

The reaction of aqueous solutions of EuIII, TbIII, and GdIII ions with Na2Hpcpa [H3pcpa = N-(4-carboxyphenyl)oxamic acid] afforded three new isostructural oxamate-containing lanthanide(III) coordination polymers of general formula {LnIII2(Hpcpa)3(H2O)5·H2O}n [Ln = Eu (1),Tb (2), and Gd(3)]. Their structure is made up of neutral zigzag chains running parallel to the [101] direction where double syn-syn carboxylate(oxamate)-bridged dilanthanide(III) pairs (Ln1 and Ln2) are linked by three Hpcpa2- ligands, one of them with the μ-κ2O,O':κO″ coordination mode and the other two with the μ3-κ2O,O':κO″:κO'''. Additionally, two of those chains are interlinked through hydrogen bonding and π-π type interactions, resulting in a porous structure with channels where water molecules are hosted. The emission properties of 1 and 2 are evaluated as a function of the temperature, exhibiting an emission in red and green, respectively. The external quantum yield for 2 is approximately 7 times that obtained for 1, indicating that the oxamate ligand is a better sensitizer for TbIII ions. The temperature dependence of the dc magnetic properties of 1-3 reveals a different magnetic behavior depending on the nature of the LnIII ion. A continuous decrease of χMT occurs for 1 upon cooling, and finally χMT tends to vanish, as expected for the thermal depopulation of the six magnetic 7FJ excited states (J = 1-6) of the EuIII ion with a nonmagnetic 7F0 ground state. χMT for 2 decreases sharply with decreasing the temperature due to the depopulation of the splitted mJ levels of the 7F7 ground state of the magnetically anisotropic TbIII ion. A very weak antiferromagnetic interaction between the magnetically isotropic GdIII ions across the double carboxylate(oxamate) bridge is responsible for the small decrease of χMT at low temperatures for 3. The dynamic (ac) magnetic properties of 2 and 3 reveal a slow magnetic relaxation with very incipient frequency-dependent χM″ signals below 6.0 K (2) and frequency-dependent χM″ peaks below 10.0 K (3) under nonzero applied dc magnetic fields, being thus new examples of field-induced single molecule magnets (SMMs).

Three 3D Lanthanide coordination polymers: Synthesis, luminescence and magnetic properties

Three 3D structures coordination polymers: [Ln(C2O4)(CH3COO)(H2O)]n (Ln = Gd, Eu, Tb) featuring a three-dimensional (3D) structure were synthesized with light-weight ligands. 1Gd owing to the higher magnetic density based on the large mass ratio (metal/ligands) and 3D structures, shows good MCE with −ΔSmmax = 39.5 J kg−1 K−1 at 2 K and ΔH = 7 T. Meanwhile, the luminescence properties and luminescence decay of 2Tb and 3Eu were investigated, the results showed that 2Tb and 3Eu present characteristic emissions of EuIII and TbIII ions.

Single-chain magnet behavior in a finite linear hexanuclear molecule.

The careful monitoring of crystallization conditions of a mixture made of a TbIII building block and a substituted nitronyl-nitroxide that typically provides infinite coordination polymers (chains), affords a remarkably stable linear hexanuclear molecule made of six TbIII ions and five NIT radicals. The hexanuclear units are double-bridged by water molecules but ab initio calculations demonstrate that this bridge is inefficient in mediating any magnetic interaction other than a small dipolar antiferromagnetic coupling. Surprisingly the hexanuclears, despite being finite molecules, show a single-chain magnet (SCM) behavior. This results in a magnetic hysteresis at low temperature whose coercive field is almost doubled when compared to the chains. We thus demonstrate that finite linear molecules can display SCM magnetic relaxation, which is a strong asset for molecular data storage purposes because 1D magnetic relaxation is more robust than the relaxation mechanisms observed in single-molecule magnets (SMMs) where under-barrier magnetic relaxation can operate.

Multifunctional properties of {CuLn} systems involving nitrogen-rich nitronyl nitroxide: single-molecule magnet behavior, luminescence, magnetocaloric effects and heat capacity.

A series of nitrogen-rich nitronyl nitroxide radical PPNIT (1)-based (PPNIT = 2-(1-(pyrazin-2-yl)-1H-pyrazole)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide) 3d-4f ring-shaped tetranuclear clusters [Ln2Cu2(hfac)10(PPNIT)2(H2O)2]·CHCl3 (LnIII = Gd 2, Tb 3, Dy 4; hfac = hexafiuoroacetylacetonate) with multifunctional properties were isolated. The magnetic behavior, luminescence and heat capacity of the 3d-4f complexes were investigated, displaying interesting multiple properties of the molecular materials. The Gd derivative shows a magnetocaloric effect with the maximum entropy change (-ΔSm) of 15.3 J kg-1 K-1 at 2 K for ΔH = 70 kOe. The Tb cluster exhibits spin glass behavior and the characteristic fluorescence emission of the TbIII ion, while the Dy cluster exhibits SMM behaviour, and the heat capacity has been investigated. Notably, in nitronyl nitroxide radical-metal systems, the investigation of diverse properties is still scarce so far. This work can pave the way towards the synthesis of multifunctional materials that combine SMM behavior, and optical or/and thermodynamic properties.

A new mononuclear terbium and copper cocrystalline nitronyl nitroxide complex: synthesis, structure and magnetic properties

One 2p-3d-4f multispin complex [Cu(hfac)(4-Me-3-NITtrz)2][Tb(hfac)4]·H2O (1) has been obtained based on a functionalized nitronyl nitroxide radical 4-Me-3-Nit-trz (in which, 4-Me-3-Nit-trz = 2-[3-(4-methyl-l,2,4-triazolyl)]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, hfac = hexafluoroacetylacetone). Complex 1 crystallizes in tetragonal system, I4¯ space group. The central CuII ion is six-coordinated in tensile octahedron configuration finished by two bidentate radical ligands and one bidentate hfac anion, while TbIII ion exhibited as distorted triangular dodecahedron geometry (D2d) finished by eight oxygen atoms from four bischelate hfac anions. Magnetic studies show that Cu(II) ion and the NO group are antiferromagnetically coupled with coupling constants of JCu–rad = 1.76~1.99 cm−1, and strong antiferromagnetic exchange interactions between the two intramolecular radicals with Jrad–rad = -12.88~-10.42 cm−1 exist in 1. In addition, alternating current (ac) magnetic susceptibilities were further measured.

Highly Oxidized States of Phthalocyaninato Terbium(III) Multiple-Decker Complexes Showing Structural Deformations, Biradical Properties and Decreases in Magnetic Anisotropy.

Presented here is a comprehensive study of highly oxidized multiple‐decker complexes composed of TbIII and CdII ions and two to five phthalocyaninato ligands, which are stabilized by electron‐donating n‐butoxy groups. From X‐ray structural analyses, all the complexes become axially compressed upon ligand oxidation, resulting in bowl‐shaped distortions of the ligands. In addition, unusual coexistence of square antiprism and square prism geometries around metal ions was observed in +4e charged species. From paramagnetic 1H NMR studies on the resulting series of triple, quadruple and quintuple‐decker complexes, ligand oxidation leads to a decrease in the magnetic anisotropy, as predicted from theoretical calculations. Unusual paramagnetic shifts were observed in the spectra of the +2e charged quadruple and quintuple‐decker complexes, indicating that those two species are actually unexpected triplet biradicals. Magnetic measurements revealed that the series of complexes show single‐molecule magnet properties, which are controlled by the multi‐step redox induced structural changes.

Enhancement of Terbium(III)-Centered Luminescence by Tuning the Triplet Energy Level of Substituted Pyridylamino-4-R-Phenoxo Tripodal Ligands.

A series of luminescent phenoxo-bridged dinuclear TbIII complexes with tripodal ligands, 2,2'-[[(2-pyridinylmethyl)imino]di(methylene)]-bis(4-R-phenol), where R = CH3 (LCH3) (I), Cl (LCl) (II), CH3O (LCH3O) (III), COOCH3 (LCOOCH3) (IV), were prepared to probe the effect of para-substitution on the phenol ring of the ligand on the TbIII luminescence. For these TbIII complexes a complete suppression of the ligand-centered fluorescence is observed, which demonstrates an efficient ligand-to-metal energy transfer. Complex IV was found to be the one that shows the greater intensity of the emission at room temperature. The obtained quantum yields follow the trend IV > II ≫ I > III. The quantum yield for II and IV is approximately five times greater than those obtained for I and III, indicating that the LCl and LCOOCH3 are better sensitizers of the TbIII ions. These results were rationalized in terms of the variation of the energy gap between the triplet level (T1) of the ligand and the emissive 5D4 level of TbIII, due to the electron-acceptor or electron-donor properties of the substituents. The τav values are in the millisecond range for all the studied complexes and resulted independent of temperature. The Commission International d'Eclairage coordinates (CIE) for all complexes are in the green color region, being insensitive to the variation of temperature. Moreover, the color purity (CP) is ca. 90% for all complexes, being ca. 100% for IV. Thus, the introduction of electron-acceptor substituents on the ligand permitted us to improve the luminescent properties of the TbIII complexes.

Two Series of Substituent‐Group‐Directed Adipate‐Based Lanthanide Coordination Polymers: Syntheses, Structures, Photoluminescence, and Magnetism

Two series of lanthanide‐organic coordination polymers (CPs) [Ln2(L1)3(H2O)4] [Ln = Nd (1), Sm (2), Eu (3), Gd (4), Tb (5), and Dy (6), H2L1 = 3‐methyl‐adipic acid] and [Ln4(L2)6(H2O)4] [Ln = Nd (7), Sm (8), Eu (9), Gd (10), Tb (11), and Dy (12), H2L2 = 3‐tert‐butyl‐adipic acid] have been synthesized by the solvothermal reactions of lanthanide salts with two types of flexible substituent adipates. All of these CPs were characterized by single‐crystal X‐ray diffraction, elemental analysis, IR spectroscopy, powder X‐ray diffraction, and thermal analysis. Structural analyses reveal that CPs 1–6 and 7–12 are isostructural, respectively. CPs 1–6 show a two‐dimensional (2D) layer constructed from the 3‐methyl‐adipate anions bridging two types of binuclear Ln2 units. The adjacent 2D layers are further extended into a three‐dimensional (3D) supramolecular framework through the hydrogen‐bonding interactions. CPs 7–12 also exhibit a 2D structure. The carboxyl groups of 3‐tert‐butyl‐adipate link four types of TbIII ions to form a one‐dimensional (1D) inorganic TbIII chain. The neighboring 1D inorganic TbIII chains are further connected by the 3‐tert‐butyl‐adipate anions to construct a 2D network. The effect of substituent groups on the formation of adipate‐based lanthanide CPs as well as the photoluminescence and magnetic properties of 1–12 were investigated in detail.