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. 2019 May 22;4(5):8731-8738.
doi: 10.1021/acsomega.8b03400. eCollection 2019 May 31.

Temperature-Induced Single-Crystal-to-Single-Crystal Transformations with Consequential Changes in the Magnetic Properties of Fe(III) Complexes

Amit Adhikary  1 , Sohel Akhtar  1 , Anand Pariyar  2 , Andrei S Batsanov  3 , Raju Mondal  1
Affiliations

Temperature-Induced Single-Crystal-to-Single-Crystal Transformations with Consequential Changes in the Magnetic Properties of Fe(III) Complexes

Amit Adhikary et al. ACS Omega. .

Erratum in

Abstract

The present article deals with an one-to-one structure-property correspondence of a dinuclear iron complex, [Dipic(H2O)FeOH]2·H2O (1) (Dipic = pyridine-2,6-dicarboxylic acid). Variable-temperature X-ray single-crystal structural analysis confirms a phase transition of complex 1 to complex 2 ([Dipic(H2O)FeOH]2) at 120 °C. Further, single-crystal-to-single-crystal (SCSC) transformation was monitored by temperature-dependent single crystal X-ray diffraction, powder X-ray diffraction, time-dependent Fourier-transform infrared spectroscopy, and differential scanning calorimetry. SCSC transformation brings the change in space group of single crystal. Complex 1 crystallizes in the C2/c space group, whereas complex 2 crystallizes in the Pi̅ space group. SCSC transformation brings the change in packing diagram as well. Complex 1 shows two-dimensional network through H-bonding, whereas the packing diagram of complex 2 shows a zigzag-like arrangement. Phase transformation not only fetches structural changes but also in the magnetic properties. Difference in Fe-O-Fe bond angles of two complexes creates notable variation in their antiferromagnetic interactions with adjacent metal centers.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Unit cell of complexes 1 (a) and 2 (b). Color code: Fe, dark yellow; C, gray; N, blue; O, red. (c) Transformation of single crystal of complex 1 to complex 2.
Figure 2
Figure 2
Molecular structure of complex 1 (a) and complex 2 (b). H atoms are omitted for clarity.
Figure 3
Figure 3
(a) Polyhedra of complex 1 and (b) polyhedra of complex 2, illustrating edge sharing between the two polyhedra. Bond distances are shown in Å.
Figure 4
Figure 4
(a) Packing diagram of complex 1 along c-axis, through extensive H-bonding network. (b) Space-fill representation of zigzag arrangement of complex 2 along a-axis. (c) Zigzag packing representation of complex 2 through H-bonding.
Figure 5
Figure 5
H-bonded dimeric unit of (a) complex 1 and (b) complex 2.
Figure 6
Figure 6
π–π interactions of (a) complex 1 and (b) complex 2.
Figure 7
Figure 7
(a, d) Hirshfeld surface of complexes 1 and 2, respectively (dnorm), showing the short contacts at the sites of H-bonding. (b, e) Fingerprints of the O···H intermolecular interactions of complexes 1 and 2, respectively. (c, f) N···H interactions of complexes 1 and 2, respectively, within the crystal packings from the single-crystal X-ray diffraction data in complexes 1 and 2, respectively. The gray zones represent all of the interactions, and the blue zones account for the corresponding O···H and N···H interactions.
Figure 8
Figure 8
Simulated and temperature-dependent experimental X-ray powder diffraction patterns observed from the sample of complex 1.
Figure 9
Figure 9
Comparison of FT-IR spectra of complex 1, complex 1 after heating, and complex 2.
Figure 10
Figure 10
DSC thermogram of complex 1 at the rate of 5 °C/min.
Figure 11
Figure 11
Energy level diagram of complexes 1 and 2, calculated through single-point DFT calculation.
Figure 12
Figure 12
Temperature-dependent dc magnetic susceptibility of complexes 1 and 2. The solid lines indicate fitting of the plots.
Figure 13
Figure 13
Model used for fitting of the χMT vs T plot for complex 1.
Figure 14
Figure 14
Temperature-dependent dc magnetic susceptibility of complexes 1 and 2. The solid lines indicate fitting of the plots considering intermolecular interactions (zJ′).
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