Neodymium coordination polymers with propionate, succinate and mixed succinate–oxalate ligands: Synthesis, structures and spectroscopic characterization

Scales, Nicholas; Zhang, Yingjie; Bhadbhade, Mohan; Karatchevtseva, Inna; Kong, Linggen; Lumpkin, Gregory R.; Li, Feng

doi:10.1016/j.poly.2015.07.065

Cited by 14 publications

(5 citation statements)

References 49 publications

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“…Only a few RE propionate based crystal structures have been reported until now; however, the published data lucidly point to the extreme structural diversity in the aforementioned system. Thus, crystal structures of 0D [Ln 2 (H 2 O) 4 Prop 6 ]· x HProp, , 1D catena-[Ln 2 (H 2 O) 3 Prop 6 ]· x H 2 O (Ln = La, Pr, Nd), − catena-[Ln 4 (HProp) 2 Prop 12 ] (Ln = Tb–Er), and most importantly, 2D catena-[Ln 2 (H 2 O) 2 Prop 6 ] (Ln = Y, Yb, Lu) , motifs have been reported. We suppose that the last type, being layered, exhibits different layer arrangements, i.e.…”

Section: Introductionmentioning

confidence: 99%

2D-Coordination Polymers Based on Rare-Earth Propionates of Layered Topology Demonstrate Polytypism and Controllable Single-Crystal-to-Single-Crystal Phase Transitions

Kendin

Tsymbarenko

2020

Crystal Growth & Design

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A series of rare-earth propionate based complexes [Ln 2 (H 2 O) 2 Prop 6 ] (Ln = Y, Ho−Lu) were synthesized in the form of two polymorphs (α and β), both being layered 2D-coordination polymers with identical geometries of the single layers. The polymorphs differ from each other in the layer arrangement, and therefore they are considered the first example of polytypes among aliphatic rare-earth carboxylates. Strategies toward the controllable crystallization of each polytype have been developed. The β polytype undergoes an irreversible single-crystal-to-single-crystal (SCSC) phase transition to the α polytype upon cooling, whereas α can be artificially converted into β via mechanical treatment. The performed DFT calculations reveal the α polytype to be more energetically favorable by 13 kJ per 1 mol of unit cells that is determined predominantly by the difference between energies of weak interlayer van der Waals interactions for the two polytypes. A low interlayer interaction energy makes it possible to use mechanical exfoliation to obtain a crystal surface of atomic smoothness suitable for mechanical decoration.

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Section: Introductionmentioning

confidence: 99%

2D-Coordination Polymers Based on Rare-Earth Propionates of Layered Topology Demonstrate Polytypism and Controllable Single-Crystal-to-Single-Crystal Phase Transitions

Kendin

Tsymbarenko

2020

Crystal Growth & Design

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“…Two main distinct series of compounds have thus been synthesized: one incorporated ditopic α,ωcarboxylates with various alkyl chain lengths, from C 2 up to C 10 . [11][12][13][14][15][16][17][18][19][20][21][22][23] The second series is based on the use of a (poly)cyclic organic ligand containing a cyclobutane 24 or cyclohexane ring, with different numbers of functionalities including two, [25][26][27][28][29][30] three, [31][32][33][34][35] four [36][37][38] or six carboxylate groups, [39][40][41] or adamantane-dicarboxylate molecules. 42,43 Other works have also described the association of 1,1′-cyclohexanediacetate or 3,3′-tetramethyleneglutate with samarium or neodymium.…”

Section: Introductionmentioning

confidence: 99%

A new series of trivalent lanthanide (Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy) coordination polymers with a 1,2-cyclohexanedicarboxylate ligand: synthesis, crystal structure, luminescence and catalytic properties

et al. 2016

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Eight lanthanide coordination polymers (Ln(,2-chdc)(form)(H2O)) have been solvothermally synthesized from the reaction of 1,2-cyclohexane dicarboxylic acid (denoted as 1,2-chdcH(2)) with trivalent metallic cations (Ce3+ (1), Pr3+ (2), Nd3+ (3), Sm3+ (4), Eu3+ (5), Gd3+ (6), Tb3+ (7) and Dy3+ (8); from a nitrate or chloride source) in a mixed H2O/N, N-dimethylformamide solvent (DMF) at T = 100-150 degrees C (form = formate ligand). Their crystal structures are similar and built up from nine-fold coordinated lanthanide cations (LnO(9) - tricapped trigonal prism), linked to each other through three Ln-O-Ln bonds (face sharing connection mode of LnO(9) polyhedra) in order to generate infinite ribbons. The coordination sphere of the lanthanide center is ensured by oxygen atoms from the 1,2-chdcH(2) ligand and formate groups. The latter come from the partial solvothermal decomposition of DMF solvent. The resulting compounds exhibit a layered structure with infinite chains of LnO(9), connected to each other via the ditopic 1,2-chdc linker. Luminescence studies (steady-state excitation, emission and time-resolved decay measurements) have been performed on the compounds bearing Ce3+, Nd3+, Sm3+, Eu3+, Tb3+, and Dy3+ cations. The Nd compound (3) was found to be efficient for isoprene (methyl-2-butadiene, CH2 = CH-C(Me)= CH2) polymerization despite the presence of water in its molecular structure, affording a highly cis stereo-regular polymer

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“…It is worth noting that no crystal structures of cerium-group lanthanide propionate monohydrates have been published in the literature to date. Instead, other compounds{[Ln 2 (H 2 O) 3 Prop 6 ]·3H 2 O} ∞ (Ln = Pr, Nd) and [Ln 2 (HProp) 2 Prop 6 ] ∞ (Ln = Nd, Sm)were described. Therefore, [Ce 2 (H 2 O) 2 Prop 6 ] ∞ , along with its lanthanum analogue, represents a novel structural type among RE propionate complexes, which are, most important, not isomorphous to yttrium and heavy lanthanide propionate monohydrates reported by us earlier …”

Section: Resultsmentioning

confidence: 99%

Polytypism and Packing-Dependent Colossal Positive and Negative Thermal Expansion in a 2D Layered Cerium-Based Coordination Polymer

Kendin,

Shaulskaya,

Tsymbarenko

2024

Crystal Growth & Design

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A two-dimensional layered coordination polymer [Ce 2 (H 2 O) 2 Prop 6 ] ∞ (Prop − = C 2 H 5 COO − ) has been crystallized in the form of two polytypes (α and β). Their structural features have been studied by means of variable-temperature single-crystal (VT-SCXRD) and powder (VT-PXRD) X-ray diffraction along with pair distribution function analysis of total X-ray scattering data (PDF). As revealed from VT-SCXRD and PDF data, α and β polytypes possess a similar local structure of layers but differ in the arrangement of layers. Single crystals and powders of [Ce 2 (H 2 O) 2 Prop 6 ] ∞ exhibit highly anisotropic thermal expansion, which is packing-dependent and drastically differs for α and β polytypes. Unit cell parameters for α demonstrate a nonlinear temperature dependence with colossal positive (α 3 CTE = +899 MK −1 ) and negative (α 1 CTE = −427 MK −1 ) linear coefficients of thermal expansion (CTEs) in the 190−210 K range. The temperature dependence of unit cell parameters for β demonstrates no colossal CTEs in the 100−300 K range. Periodic DFT-D calculations have shown the weakening of interlayer interactions (cohesive energies for α and β are 149 and 144 mJ/m 2 at 100 K, and 111 and 129 mJ/m 2 at 300 K, respectively) and relaxation of stressed layers upon heating.

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Neodymium coordination polymers with propionate, succinate and mixed succinate–oxalate ligands: Synthesis, structures and spectroscopic characterization

Cited by 14 publications

References 49 publications

2D-Coordination Polymers Based on Rare-Earth Propionates of Layered Topology Demonstrate Polytypism and Controllable Single-Crystal-to-Single-Crystal Phase Transitions

2D-Coordination Polymers Based on Rare-Earth Propionates of Layered Topology Demonstrate Polytypism and Controllable Single-Crystal-to-Single-Crystal Phase Transitions

A new series of trivalent lanthanide (Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy) coordination polymers with a 1,2-cyclohexanedicarboxylate ligand: synthesis, crystal structure, luminescence and catalytic properties

Polytypism and Packing-Dependent Colossal Positive and Negative Thermal Expansion in a 2D Layered Cerium-Based Coordination Polymer

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