Issue 4, 2015

Highly pH-dependent synthesis of two novel three-dimensional dysprosium complexes with interesting magnetic and luminescence properties

Abstract

Two novel Dy-based MOFs, namely, {[Dy2(PA)3(H2O)3(DMF)]·(DMF)2·(H2O)}n (1) and [Dy2(PA)3(H2O)2(DMF)2]·(DMF)3·(H2O)}n (2) (H2PA = pamoic acid), were solvothermally synthesized from the reaction of Dy(NO3)3 and H2PA at different pH values. Interestingly, both complexes can be obtained simultaneously within the pH range of 5.0–6.2, while higher pH values (6.2–7.0) promote the formation of compound 1 and lower pH values (2.0–5.0) tend to produce pure complex 2. Single-crystal X-ray diffraction studies indicate that 1 and 2 are both three-dimensional frameworks composed of dinuclear Dy(III) subunits featuring pcu networks with the point symbol of {412·63}. Significantly, their slight structure difference results in these two compounds showing completely different magnetic properties. Variable temperature magnetization measurements (χMTT) demonstrate ferromagnetic interactions in compound 1, while possible antiferromagnetic interactions were observed in compound 2. Alternating current (ac) susceptibility measurements indicate that both the in-phase (χ′) and out-of-phase (χ′′) components showed frequency dependence in compound 1, suggesting that there is a slow relaxation behavior of the magnetization, which is typical of single-molecule magnets (SMMs), while no out-of-phase ac signal was noticed for 2. Furthermore, both 1 and 2 exhibit the characteristic luminescence of Dy3+ upon excitation at 365 nm, but with different intensities. The reasons for such magnetic and luminescence differences are discussed in detail.

Graphical abstract: Highly pH-dependent synthesis of two novel three-dimensional dysprosium complexes with interesting magnetic and luminescence properties

Supplementary files

Article information

Article type
Paper
Submitted
06 Oct 2014
Accepted
20 Nov 2014
First published
24 Nov 2014

CrystEngComm, 2015,17, 846-855

Author version available

Highly pH-dependent synthesis of two novel three-dimensional dysprosium complexes with interesting magnetic and luminescence properties

L. Zhang, S. Lu, C. Zhang, C. Du and H. Hou, CrystEngComm, 2015, 17, 846 DOI: 10.1039/C4CE02023E

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