4.7 Article

Temperature-controlled synthesis and luminescent properties of two novel coordination polymers modeled by hexa-carboxylate ligand derived from cyclotriphosphazene

Journal

DALTON TRANSACTIONS
Volume 42, Issue 7, Pages 2588-2593

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/c2dt32431h

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Funding

  1. National Natural Science Foundation of China [21101066, 20871049]
  2. Wuhan Science and Technology Bureau [201271031384]

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Solvothermal reactions of hexakis(4-formylphenoxy)cyclotriphosphazene (H(6)L1) with Cd(NO3)(2)center dot 4H(2)O in H2O/DMF under different synthesis temperatures produced two new compounds, namely, {[Cd-3(C42H24O18P3N3) (H2O)(7)].xGuest}(n) (1), and {[Cd-2(C42H24O18P3N3) (H2O)(2)].xGuest}(n) (2). Compound 1 exhibits a novel 3D framework adopting 2,4,6-connected 3-nodal topology with the point (Schlafli) symbol {4(4).6(2)}{4(5).6(2).8(8)}{4} constructed from the joint of neutral Cd-2 SBUs, mono-Cd ions and L1 ligands. Compound 2 reveals a 2D crystal structure exhibiting a 3,6-connected 2-nodal kgd topology with the point (Schlafli) symbol {4(3)}(2){4(6).6(6).8(3)} constructed from the connection of Cd centers and L1 ligands. In these two compounds, the ligands L1 are fully deprotonated, whose six extended carboxyl arms connect six different/same metallic nodes to form high dimensional frameworks. The variable reaction temperature must be responsible for the higher coordination number and versatile coordination modes of carboxylates in 1 compared to the ones in 2, resulting in the formation of a distinct crystal structure. In the solid state, both complexes are photoluminescent (LMCT) at room temperature.

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