Chapter 4 - Jacobs University

More documents

Recommendations

Info

<strong>Chapter</strong> 4 16-Iron Metal Center Nanocluster Table 4.1: Crystal Data and Structure Refinement for Li 4 K 16 [P 8 W 48 O 184 Fe 16 (OH) 28 (H 2 O) 4 ]∙66H 2 O∙2KCl (2a) and Na 9 K 11 [P 8 W 48 O 184 Fe 16 (OH) 28 (H 2 O) 4 ]∙100H 2 O (2b) 2a 2b emp formula H 164 Cl 2 Fe 16 K 18 Li 8 O 282 P 8 W 48 H 236 Fe 16 K 11 Na 9 O 316 P 8 W 48 fw (g/mol) 15473.7 16300.9 crystal system Orthorhombic Monoclinic space group(No.) Pnnm (58) C2/c (15) a (Å) 36.3777(9) 46.5522(4) b (Å) 13.9708(3) 20.8239(18) c (Å) 26.9140(7) 27.8261(2) vol (Å 3 ) 13678.4(6) 26765.34(4) Z 2 4 temp (°C) -100 -90 d calcd (Mg m -3 ) 3.76 3.945 abs coeff. (mm -1 ) 21.37 21.74 transmission 0.381 and 0.128 0.355 and 0.220 Data / parameters 14333 / 492 29084 / 1584 Goodness-of-fit on F 2 1.02 1.08 R [I > 2s(I)] 0.059 0.109 R w (all data) 0.183 0.303 79
<strong>Chapter</strong> 4 16-Iron Metal Center Nanocluster 4.4 Results and discussion 4.4.1 Synthesis and structure Although the P 8 W 48 cluster had been known for more than 20 years, 5 only recently the first examples of metal-containing derivatives have been reported. Pope’s group prepared the first lanthanide derivative, {Ln 4 (H 2 O) 28 [KÌP 8 W 48 O 184 (H 4 W 4 O 12 ) 2 Ln 2 (H 2 O) 10 ] 13- } x (Ln = La, Ce, Pr, Nd), 6 and Kortz and coworkers isolated the first transition metal derivative, the 20-copper(II) containing [Cu 20 Cl(OH) 24 (H 2 O) 12 (P 8 W 48 O 184 )] 25- 7 (see also the report on the Cu 20 -azide derivative [P 8 W 48 O 184 Cu 20 (N 3 ) 6 (OH) 18 ] 24- , 8 ), while Müller et al. discovered [K 8 Ì{P 8 W 48 O 184 }{V V 4V IV 2O 12 (H 2 O) 2 } 2 ] 24- containing two cationic V 6 type mixed-valence clusters and formed by an unprecedented nucleation process. 9 Very recently Kortz et al. reported {K(H 2 O)} 3 {Ru(p-cymene)(H 2 O)} 4 P 8 W 49 O 186 (H 2 O) 2 ] 27- which represents the first organometallic derivative of P 8 W 48 . 10 Here we report on the iron derivative [P 8 W 48 O 184 Fe 16 (OH) 28 (H 2 O) 4 ] 20- (2), which was identified independently in Bremen 11 and Bielefeld. Polyanion [P 8 W 48 O 184 Fe 16 (OH) 28 (H 2 O) 4 ] 20- (2) was isolated as the mixed cation salts Li 4 K 16 [P 8 W 48 O 184 Fe 16 (OH) 28 (H 2 O) 4 ]∙66H 2 O∙2KCl (2a) and Na 9 K 11 [P 8 W 48 O 184 Fe 16 (OH) 28 (H 2 O) 4 ]∙100H 2 O (2b), see Experimental Section. Polyanion 2 contains an unprecedented {Fe 16 (OH) 28 (H 2 O) 4 } 20+ cluster in the cavity of P 8 W 48 with 16 edgeand corner-sharing FeO 6 octahedra being grafted to the inner surface of the “host” ( Figures 4.3 and 4.4). 80
Page 1 and 2:
Synthesis, Structure and Properties
Page 3 and 4:
"The greatest book of philosophy, w
Page 5 and 6:
system, space group I4/m, unit cell
Page 7 and 8:
Acknowledgements The accomplishment
Page 9 and 10:
teaching, and Professor Maravanji S
Page 11 and 12:
2.1.2 Single crystal X-ray diffract
Page 13 and 14:
5.5 Conclusion…………………
Page 15 and 16:
9.1.6.1 Results and discussion…
Page 17 and 18:
9.3.5 Synthesis of K 12 [Hf 4 (µ 2
Page 19 and 20:
Crespo………………………
Page 21 and 22:
Figure 5.4 ORTEP view of the asymme
Page 23 and 24:
Figure 9.6 31 P NMR of 7a in H 2 O/
Page 25 and 26:
Figure 9.34 TGA spectrum of 17a…
Page 27 and 28:
Figure 9.62 FTIR spectrum of 23a…
Page 29 and 30:
Table 9.6 Crystal data and structur
Page 31 and 32: Chapter 1 Introduction heteropolyan
Page 33 and 34: Chapter 1 Introduction 1.3 Structur
Page 35 and 36: Chapter 1 Introduction C) Keggin a-
Page 37 and 38: Chapter 1 Introduction shows no suc
Page 39 and 40: Chapter 1 Introduction α-[P 2 W 18
Page 41 and 42: Chapter 1 Introduction Figure 1.7 B
Page 43 and 44: Chapter 1 Introduction [P 2 W 18 O
Page 45 and 46: Chapter 1 Introduction 1.5.3 Medici
Page 47 and 48: Chapter 1 Introduction (17) Evans,
Page 49 and 50: Chapter 1 Introduction (48) Mizuno,
Page 51 and 52: Chapter 1 Introduction (84) Isabell
Page 53 and 54: Chapter 2 were block-diagonal least
Page 55 and 56: Chapter 2 Experimental 2.2.3 Synthe
Page 57 and 58: Chapter 2 Experimental 2.2.7 Synthe
Page 59 and 60: Chapter 2 Experimental 2.2.11 Synth
Page 61 and 62: Chapter 2 Experimental 2.3Reference
Page 63 and 64: Chapter 3 The Wheel-Shaped Cu 20 in
Page 65 and 66: Chapter 3 The Wheel-Shaped Cu 20 3.
Page 69 and 70: Chapter 3 The Wheel-Shaped Cu 20 Fi
Page 71 and 72: Chapter 3 The Wheel-Shaped Cu 20 Cu
Page 75 and 76: Chapter 3 The Wheel-Shaped Cu 20 20
Page 77 and 78: Chapter 4 16-Iron Metal Center Nano
Page 81: Chapter 4 16-Iron Metal Center Nano
Page 93 and 94: Chapter 5 Organoruthenium POM Chapt
Page 95 and 96: Chapter 5 Organoruthenium POM 5.2 S
Page 97 and 98: Chapter 5 Organoruthenium POM 5.3 X
Page 99 and 100: Chapter 5 Organoruthenium POM 5.4 R
Page 101 and 102: Chapter 5 Organoruthenium POM The f
Page 103 and 104: Chapter 5 Organoruthenium POM On th
Page 105 and 106: Chapter 5 Organoruthenium POM Figur
Page 107 and 108: Chapter 5 Organoruthenium POM (11)
Page 109 and 110: Chapter 6 U-peroxo-Polyoxometalate
Page 127 and 128: Chapter 7 Pt-containing Polyoxometa
Page 133 and 134:
Chapter 7 Pt-containing Polyoxometa
Page 135 and 136:
Page 137 and 138:
Page 139 and 140:
Page 141 and 142:
Chapter 8 Collaborative Work Chapte
Page 143 and 144:
Chapter 8 Collaborative Work 8.2.1
Page 145 and 146:
Chapter 9 Unpublished Results Figur
Page 147 and 148:
Chapter 9 Unpublished Results solid
Page 149 and 150:
Page 151 and 152:
Chapter 9 Unpublished Results 9.1.3
Page 153 and 154:
Page 155 and 156:
Page 157 and 158:
Page 159 and 160:
Page 161 and 162:
Page 163 and 164:
Chapter 9 Unpublished Results There
Page 165 and 166:
Page 167 and 168:
Page 169 and 170:
Page 171 and 172:
Page 173 and 174:
Chapter 9 Unpublished Results Table
Page 175 and 176:
Page 177 and 178:
Page 179 and 180:
Page 181 and 182:
Page 183 and 184:
Page 185 and 186:
Page 187 and 188:
Page 189 and 190:
Page 191 and 192:
Page 193 and 194:
Page 195 and 196:
Page 197 and 198:
Page 199 and 200:
Page 201 and 202:
Chapter 9 Unpublished Results exhib
Page 203 and 204:
Page 205 and 206:
Page 207 and 208:
Page 209 and 210:
Page 211 and 212:
Page 213 and 214:
Page 215 and 216:
Page 217 and 218:
Page 219 and 220:
Chapter 9 Unpublished Results The d
Page 221 and 222:
Page 223 and 224:
Chapter 9 Unpublished Results 23a (
Page 225 and 226:
Page 227 and 228:
Page 229 and 230:
Page 231 and 232:
Page 233 and 234:
Page 235 and 236:
Page 237 and 238:
Curriculum Vitae SIB SANKAR MAL Dep
Page 239 and 240:
EDUCATION PhD Jacobs University (20
Page 241 and 242:
POSTER, ORAL PRESENTATION 1. Poster
Page 243 and 244:
6. “Two Iron-Containing Tungstoge
Page 245 and 246:
Appendix
Page 247 and 248:
Page 249 and 250:
Appendix
Page 251 and 252:
show all

Chapter 4 - Jacobs University

Create successful ePaper yourself

Delete template?

Save as template?