Crystal Structure and Luminescent Property of a New Heterometallic Coordination Polymer Based on 1D –{Ca–(COO)₂–Cu–(COO)₂–Ca}_n– Chains

Abstract

A new heterometallic coordination polymer, namely [CuCa(tdc) 2 (DMA)(H 2 O) 2 ] n (1, H 2 tdc D 2,5-thiophenedicarboxylic acid, DMA D N, N-dimethylacetamide) has been solvothermally synthesized by the reactions of CuCl 2 , CaCl 2 , and H 2 tdc. X-ray structural analysis reveals that compound 1 features a 3D heterometallic framework based on one-dimensional{Ca-(COO) 2 -Cu-(COO) 2 -Ca} n -chains. Moreover, the luminescent properties of compound 1 and desolvated 1 were also investigated at room temperature.

Lanthanide Contraction in Action: Structural Variations in 13 Lanthanide(III) Thiophene-2,5-dicarboxylate Coordination Polymers (Ln = La–Lu, Except Pm and Tm) Featuring Magnetocaloric Effect, Slow Magnetic Relaxation, and Luminescence-Lifetime-based Thermometry

“…There are two main approaches toward realizing luminescent thermometry. One approach builds upon the temperature dependence of steady-state luminescence properties such as band shift, change in their band widths, and intensity of bands, − the last of which is by far the most employed in thermometric studies on Ln-CPs. − …”

“…Various polar aprotic solvents with high boiling points, namely DMF ( N , N′ -dimethylformamide), DMA ( N , N′ -dimethylacetamide), DEF ( N , N′ -diethylformamide), DMSO (dimethyl sulfoxide), NMP ( N -methyl-2-pyrrolidone or 1-methylpyrrolidin-2-one), etc., have been used for the synthesis of coordination networks, especially of MOFs. , Among the aforementioned aprotic polar solvents DMA has been one of the least employed to date. − Additionally, systematic studies of their steric effects on the coordination behaviors of Ln 3+ centers are rather uncommon; hence, the first goal that we set out for this study is the determination of what the coordination steric effect of the ancillary DMA solvent is on the self-assembly of lanthanide­(III) 2,5-thiophenedicarboxylates. To this end, we have prepared 13 highly related Ln-CPs, in which Ln = La–Lu except Pm and Tm, with the general formulas of [Ln 2 (2,5-TDA) 3 (DMA) 2 (H 2 O)] n (group A of Ln-CPs 1 – 4 ) and [Ln 2 (2,5-TDA) 3 (DMA) 2 ] n (group B of Ln-CPs 5 – 13 ), wherein 2,5-TDA 2– = 2,5-thiophedicarboxylate dianion and Ln = La ( 1 ), Ce ( 2 ), Pr ( 3 ), Nd ( 4 ), Sm ( 5 ), Eu ( 6 ), Gd ( 7 ), Tb ( 8 ), Dy ( 9 ), Ho ( 10 ), Er ( 11 ), Yb ( 12 ), Lu ( 13 ).…”

Dual-Ligand Strategy Employing Rigid 2,5-Thiophenedicarboxylate and 1,10-Phenanthroline as Coligands for Solvothermal Synthesis of Eight Lanthanide(III) Coordination Polymers: Structural Diversity, DFT Study, and Exploration of the Luminescent Tb(III) Coordination Polymer as an Efficient Chemical Sensor for Nitroaromatic Compounds

“…Numerous polar aprotic solvents such as N , N ′-dimethylformamide (DMF), N , N ′-dimethylacetamide (DMA), N , N ′-diethylformamide (DEF), dimethyl sulfoxide (DMSO), and N -methyl-2-pyrrolidone (NMP or 1-methylpyrrolidin-2-one) having high boiling points have been extensively used for the self-assembly of coordination polymers/metal organic frameworks. , Among the aforementioned solvents, N , N ′-dimethylacetamide (DMA) and dimethyl sulfoxide (DMSO) are the least explored. − …”