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Paramagnetic and Luminescent Properties of Gd Ascorbate Coordination Polymers
Gadolinium-based contrast agents (GBCAs) are the gold standard as MRI probes but are nowadays facing medical limitations and environmental concerns. To address these issues, novel strategies focus on the optimization of Gd(III)-based probes. One promising approach involves incorporating Gd(III) into nanoparticles, particularly coordination polymers, which offer improved relaxivity. In this study, we explore the self-assembly of Gd(III) ions with ascorbate ligand, forming extended coordination polymer architectures. Our investigation focuses on understanding the impact of nanoparticles’ growth and aggregation on their relaxivity properties. Notably, the controlled aggregation process leads to a different distribution of the Gd(III) in the surface and in the bulk of the nanoparticles, mainly responsible for their longitudinal relaxivity. Additionally, the introduction of Eu(III) into the network enables the development of a dual-modal probe with paramagnetic and optical features.
Journal Article
Coordination Polymer Based on a Triangular Carboxylate Core Fesub.6 and an Aliphatic Diamine
Interaction of the pre-organized complex of iron(II) trimethylacetate and 1,10-phenanthroline (phen) [Fe[sub.2](piv)[sub.4](phen)[sub.2]] (1) (piv = (Me)[sub.3]CCO[sub.2] [sup.−])) with 1,6-diaminohexane (dahx) in anhydrous acetonitrile yielded a 1D coordination polymer [Fe[sub.3]O(piv)[sub.6](dahx)[sub.1.5]]n (2) and an organic salt of pivalic acid (H[sub.2]dahx)(piv)[sub.2] (3). The structure of the obtained compounds was determined by single-crystal X-ray diffraction analysis. The phase purity of the complexes was determined by powder X-ray diffraction analysis. According to the single-crystal X-ray analysis, coordination polymer 2 is formed due to the binding of a triangular carboxylate core Fe[sub.3](μ[sub.3]-O)(μ-piv)[sub.6] with an aliphatic diamine ligand. Thermal behavior was investigated for compounds 1 and 2 in an argon atmosphere.
Journal Article
Statistical Analysis of Copperalkane-Based Complexes and Coordination Polymers
The prediction of the metal cluster within a coordination polymer or complex, as well as the dimensionality of the resulting polymer or complex (i.e., 0D, 1D, 2D, or 3D), is often challenging. This is the case for Ph[sub.2]P(CH[sub.2])[sub.m]PPh[sub.2] ligands (1 ≤ m ≤ 8) and CuX salts, particularly for X = I. This work endeavors a systematic statistical analysis combining studies in the literature and new data, mapping the nature of the resulting CuI aggregates with eight different diphoshphines in 2:1, 3:2, 1:1, 2:3, and 1:2 CuI:Ph[sub.2]P(CH[sub.2])[sub.m]PPh[sub.2] molar ratios as a function of m, which lead to either pure products or mixtures. Several trends are made relating stoichiometry and chain length to the CuI cluster formed (i.e., globular vs. quasi-planar). Four new X-ray structures were determined: [Cu[sub.3]I[sub.2](L1)[sub.3]]I, Cu[sub.3]I[sub.3](L2)[sub.2], Cu[sub.2]I[sub.2](L6)[sub.2], and Cu[sub.4]I[sub.4](L8)[sub.2], where m is, respectively, 1, 2, 6, and 8, in which the Cu[sub.x]I[sub.y] central aggregates adopt triangular bipyramid, diamond, rhomboid, and cubane shaped motifs, respectively. Photophysical measurements assisted the establishment of trends considering the paucity of the crystallographic structures. During this study, it was also found that the 0D-complex Cu[sub.2]I[sub.2](Ph[sub.2]P(CH[sub.2])[sub.5]PPh[sub.2])[sub.2] exhibits thermally activated delayed fluorescence.
Journal Article
