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Lanthanide-Based Coordination Polymers Assembled by a Flexible Multidentate Linker: Design, Structure, Photophysical Properties, and Dynamic Solid-State Behavior

Authors

  • Claire Marchal Dr.,

    1. Laboratoire de Reconnaissance Ionique et Chimie de Coordination, Service de Chimie Inorganique et Biologique (UMR-E 3 CEA-UJF), CEA/DSM/INAC, CEA-Grenoble, 38054 Grenoble, Cedex 09 (France)
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  • Yaroslav Filinchuk Dr.,

    1. Swiss–Norwegian Beam Lines (SNBL), European Synchrotron Radiation Facility (ESRF) rue Jules Horowitz, 38043 Grenoble (France)
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  • Xiao-Yan Chen Dr.,

    1. Laboratoire de Reconnaissance Ionique et Chimie de Coordination, Service de Chimie Inorganique et Biologique (UMR-E 3 CEA-UJF), CEA/DSM/INAC, CEA-Grenoble, 38054 Grenoble, Cedex 09 (France)
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  • Daniel Imbert Dr.,

    1. Laboratoire de Reconnaissance Ionique et Chimie de Coordination, Service de Chimie Inorganique et Biologique (UMR-E 3 CEA-UJF), CEA/DSM/INAC, CEA-Grenoble, 38054 Grenoble, Cedex 09 (France)
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  • Marinella Mazzanti Dr.

    1. Laboratoire de Reconnaissance Ionique et Chimie de Coordination, Service de Chimie Inorganique et Biologique (UMR-E 3 CEA-UJF), CEA/DSM/INAC, CEA-Grenoble, 38054 Grenoble, Cedex 09 (France)
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Abstract

Flexible director: A flexible multidentate linker containing picolinate chromophores directs the selective formation of luminescent 1D lanthanide-based polymers. Partial protonation significantly decreases the preorganization of the linker, thus leading to supramolecular 1D and 2D isomers (see scheme). The lanthanide-containing 1D polymers undergo reversible structural modification in the hydration/dehydration process, which is also associated with significant differences in the luminescence emission.

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Four picolinate building blocks were implemented into the multidentate linker N,N′,N′-tetrakis[(6-carboxypyridin-2-yl)methyl]butylenediamine (H4tpabn) with a linear flexible spacer to promote the assembly of lanthanide-based 1D coordination polymers. The role of the linker in directing the geometry of the final assembly is evidenced by the different results obtained in the presence of Htpabn3− and tpabn4− ions. The tpabn4− ion leads to the desired 1D polymer {[Nd(tpabn)]H3O⋅6 H2O} (12). The Htpabn3− ion leads to the assembly of TbIII and ErIII ions into 1D zigzag chains of the general formula {[M(Htpabn)]⋅x H2O} (M=Tb, x=14 (1); M=Tb, x=8 (11); M=Er, x=14 (2); M=Er, x=5.5 (4)), a 2D network is formed by the EuIII ion (i.e., {[Eu(Htpabn)]⋅10 H2O} (7)), and both supramolecular isomers (1D and 2D) are obtained by the TbIII ion. The high flexibility of the polymeric chains results in a dynamic behavior with a solvent-induced reversible structural transition. The TbIII- and EuIII-containing polymers display high-luminescence quantum yields (38 and 18 %, respectively). A sizeable near-IR luminescence emission is observed for the ErIII- and NdIII-containing polymers when lattice water molecules are removed.

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