Synthesis and Structural Characterization of ... - Jacobs University

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Chapter 4 Unpublished Results Elemental analyses were carried out by Zentralabteilung für chemische Analysen, Forschungszentrum Jülich GmbH, 52425 Jülich, Germany. 4.3. X‐ray Crystallography The crystallographic data are summarized in Table 4.1. Table 4.1. Crystal Data and Structure Refinement for KLiNa-24 and KLiNa-25. Code KLiNa-24 KLiNa-25 Empirical formula K 8.5 Li 0.5 Na 0.5 Eu 4.5 Fe 16 P 8 W 49 O 313 H 221 K 9 LiNaGd 4 Fe 16 P 8 W 49 O 293 H 181 MW 16411.9 16031.3 Crystal system Triclinic Triclinic Space group (no.) P1̅ (2) P1̅ (2) aÅ 26.6844(12) 26.7348(18) bÅ 27.2118(11) 27.1921(15) cÅ 27.4619(10) 27.4514(17) ° 61.803(2) 61.840(2) ° 77.476(2) 77.508(3) ° 63.977(2) 64.028(3) V/Å 3 15791.6(11) 15816.3(17) Z 2 2 T/ ºC -100 -100 λÅ 0.71073 0.71073 D/ Mg m -3 3.452 3.366 μ/ mm -1 19.62 19.54 R[I >2sigma(I)] a 0.101 0.077 R w (all data) b 0.271 0.232 __________________________ a R = ∑|F o | – |F c | |∑| |F o |. b R w = {∑[w(F o 2 – F c 2 ) 2 ] / ∑[w(F o 2 ) 2 ]} 1/2 . 151
Chapter 4 Unpublished Results 4.4. Results and Discussion We have synthesized and structurally characterized the open-ring 16-iron(III)-containing polyanions [Fe 16 O 2 (OH) 23 (H 2 O) 9 P 8 W 49 O 189 Ln 4 (H 2 O) 19 ] 11− (Ln = Eu (24), and Gd (25)) in a one-pot reaction of Ln 3+ , Fe 3+ and P 8 W 48 in acidic aqueous medium and in the presence of hydrogen peroxide. Polyanions 42 and 25 crystallize as hydrated mixed salts (KLi-24) and (KLi-25), both in the triclinic space group P1̅, see experimental section. These salts were characterized in the solid state by FTIR, single-crystal XRD, TGA and elemental analysis. Polyanions 24 and 25 are isostructural. They contain the [Fe 16 O 2 (OH) 23 (H 2 O) 9 ] 21+ nanocluster coordinating to a novel open-ring shaped [P 8 W 49 O 189 ] 44− (P 8 W 49 ) forming {Fe 16 O 2 (OH) 23 (H 2 O) 9 P 8 W 49 O 189 } fragment (Fe 16 P 8 W 49 ) which is in turn coordinated to four lanthanide(III) cations (see Figure 4.2). In other words, four lanthanide(III) cations and a [Fe 16 O 2 (OH) 23 (H 2 O) 9 ] 21+ cluster are being grafted to the inner surface of the unprecedented open-ring P 8 W 49 “host”. Polyanions 24 and 25 exhibit a low symmetry C s structure. The structures of the previously reported (Fe 16 P 8 W 48 ) 10 and polyanions 24 and 25 are very similar but not identical. In relation with (Fe 16 P 8 W 48 ), the structures of polyanions 24 and 25 are derived from the Fe 16 cluster and the P 8 W 48 unit. They consist of 16 Fe 3+ centers which are arranged as edge and corner-shared FeO 6 octahedra grafted to the inner surface of the P 8 W 49 “host”. Each of the 16 Fe 3+ centers is bound to P 8 W 49 via a Fe–O(W) and a Fe–O(P) bond (see Figure 4.2). 152
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