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A. V. Pavlishchuk

SUPRAMOLECULAR ASSEMBLIES AND COORDINATION POLYMERS BASED ON HOMO- AND HETEROMETALLIC METALLACROWN BUILDING BLOCKS. A. V. Pavlishchuk. Kiev National Taras Shevchenko University. obtaining of high nuclearity systems: two approaches. Self-assembly non-predictable structure

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A. V. Pavlishchuk

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  1. SUPRAMOLECULAR ASSEMBLIES AND COORDINATION POLYMERS BASED ON HOMO- AND HETEROMETALLIC METALLACROWN BUILDING BLOCKS A. V. Pavlishchuk Kiev National Taras Shevchenko University

  2. obtaining of high nuclearity systems: two approaches • Self-assembly • non-predictable structure • non-predictable properties • Building blocks or ‘’complex as ligand’’ • predictable structure to certain extent • properties of resulting compound are predetermined by the building block • possibility to combine several properties in one compound (important for multifunctional materials creation) 2

  3. Why have wechosen metallacrowns? Hydroxamate MC complexes can be classified into several types: 9-MC-3, 12-MC-4 and 15-MC-5 12-MC-4 and 15-MC-5 possess vacant apical coordination positions. Almost planar, minimal steric hindrances Stable in solutions over a wide range of conditions (pH, solvent) Easily obtained with high yields in one-step reactions Possess potentially useful properties, such as ability to selective recognition of anions, cations and neutral molecules, bioactivity, non-trivial magnetic and catalytic properties Metallacrowns (MC) are polynuclear assemblies, which are usually obtained on the basis hydroxamic acids 9-MC-3 12-MC-4 15-MC-5 3

  4. STARTING COMPOUNDS [Cu5(ahpha)4](ClO4)2 Building block 1 [Cu5L4]2+: 12-MC-4 The distance between mean planes LnCu5 of two neighbouring MC units is ~6Å [GdCu5(GlyHA)5]2(SO4)3 Building block 2 [LnCu5(L1)5]3+: 15-MC-5 (Ln3+ = Sm3+,Eu3+,Gd3+,Nd3+,Pr3+,Ho3+,Dy3+) 4

  5. Linkers • polycarboxylates and others • anionic mononuclear complexes K2Cu(C2O4)2 K3Cr(C2O4)3 5

  6. Cu5 complexes as building blocks Complex 1 Complex 1a + DMF/H2O DMF/MeOH base Cu3 - O10’ 2.894(5)Å Cu3 – O9’ 2.988(3)Å π-π stacking: 3.279(4)Å. Selected hydrogen bonds O14-H8D = 1.941(2) Å,O15-H11D = 2.035(4) Å No π-π stacking. Selected hydrogen bonds O14-H2C = 1.999(4) Å, O16-H9 = 1.813(3) Å, O16-H8C = 1.996(5) Å 6

  7. complexes 1 AND 1a: packing Complex 1 Volume of the voids: 396.7Å3 or 20.6%,which corresponds to 0.085 cm3/g voids along axis a 16.56.1 Å All void volumes calculated by Platon for probe molecule with r = 1.4 Å assuming that the structure is retained afterdesolvatation Complex 1a Volume of the voids is 1879.1 Å3 or 18.7% which corresponds to 0.073 cm3/g voids along axis b 12.36.6 Å 7

  8. Cu5 complexes as building blocks + DMF/H2O base Cu1 – O6’ 2.677(4)Å.Selected hydrogen bonds: O13-H19A (1.9462(1)Å), O16-H19B (1.8892(1)Å), O17-H10 (1.7992(1)Å) Complex 2 [Cu5(ahpha)4(p-C8H4O4).2H2O]2 Volume of the voids is 441.3Å3 or 11.8%(Platon calculations), whichcorresponds to 0.049 cm3/g 8

  9. Cu5 complexes as building blocks DMF/Et2O DMF/MeOH + Voids 10x11 Å.Volume of the voids is 5411.9 Å3or 40.7%(Platon calculations), which corresponds to 0.243 cm3/g Complex 3a Two deprotonated maleic acids are bounded to one metallacrown unit Cu3-O8 = 2.574(2) Complex 3 Deprotonated maleic acid are bounded to metallacrown units via hydrogen bonds: O10-H6 = 1.955(4)Å, O11-H11A = 1.747(3)Å, O8-H5C = 2.036(4)Å NONPOROUS 9

  10. Cu5 complexes as building blocks + DMF/H2O Complex 4 This complex is the first example of metallacrown trimerization Channels 9  12 Å. According to the Platon calculations pore volume is 3343.35(4)Å3 or 26.6 %, which corresponds to 0.129 cm3/g 10

  11. SORPTION PROPERTIES of obtained assemblies Isotherms of MeOH (left), EtOH (center) and n-hexane (right) sorption by activated complexes 1 and 2 EtOH 11 Ethanol sorption by activated complex 4

  12. Magnetic PROPERTIES of obtained assemblies gCr = 1.959 (fixed) Cu1 Cu2 Cu5 Cu4 Cu3 χMT vs. T plot for complexes 1 (□) and 2: (○) χMT vs. T plot for complex 4 12 J2 J1 J1 J2 J2 J2 J1 J1

  13. LnCu5 complexes as building blocks DMF/H2O DMF/H2O + Two isomers of coordination polymer were isolated from the reaction mixture Complex 5a Complex 5 Complex 5 is 1D coordination polymer, which chains are packed into the 2D net due to the extended system of hydrogen bonds Complex 5a is 2D coordination polymer 13

  14. LnCu5 complexes as building blocks DMF/H2O + Average distance Cu – Cu is 4.568Å, while Cu-Gd = 3.869 Å Complex 6 Complex 6 is 1D coordination polymer, which chains are packed into the 2D net due to the large system of hydrogen bonds 14

  15. {[GdCu5(GlyHA)5] 2[m-C8H4O4]3}n : magnetic properties Cu1 Cu5 Cu4 Cu2 Gd Distance between mean planes GdCu5 of two neighbouring MC units is about 7.5 Å. Cu3 χMT vs. T plot for complex 6 J1=-61.0 cm-1, J2= +0.6 cm-1,zJ=-0.035 cm-1, gGd=2.033, gCu=2.1, TIP=0.0011,R2 = 3.01.10-5 This complex is the first example of 15-MC-5 systems, for which exchange parameters are reported 15 J1 J1 J2 J2 J2 J2 J2 J1 J1 J1

  16. LnCu5 complexes as building blocks DMF/H2O + K3Cr(C2O4)3 Complex 7 Volume of the voids is 4884.2 Å3 or 19.8 % (Platon calculations) which corresponds to 0.074 cm3/g Complex 7 is 1D zig-zag coordination polymer, which chains are packed into the 2D net due to the large system of hydrogen bonds Voids along axis c5.6x9.9Å 16

  17. {[GdCu5(GlyHA)5] [Cr(C2O4)3]}n : magnetic properties Cu1 Cu5 Cu4 Cu2 Gd Cu3 Average distance Cu – Cu is 4.571Å, while Cu-Gd = 3.878 Å Contacts: Cu – Cr is 5.432Å, while Gd-Cr = 5.952 Å J1=-25.0 сm-1, J2= +1.0 cm-1, JCu-Cr= -12.0 cm-1, JGd-Cr= +0.5 cm-1 zJ=-0.009 сm-1, gGd=2.033 (fixed), gCu=2.1 (fixed), gCr=1.959 (fixed), TIP=0.0019, R2 = 3.86.10-5 17 J1 J1 J2 J2 J2 J2 J2 J1 J1 J1

  18. LnCu5 complexes as building blocks DMF/H2O + K2Cu(C2O4)2 Complex 8 Voids along axis a6.6x9.67Å Complex 8 is 2D coordination polymer Average distances inside MC unitCu – Cu is 4.559Å, while Cu-Gd = 3.915 Å Average distances outside MC unitCu – Cu is 3779Å, while Cu-Gd = 5.736 Å Volume of the voids is 2139.3 Å3 or 12.5 % (Platon calculations), which corresponds to 0.055 cm3/g 18

  19. RESULTS & OUTLOOKS • The possibility of using metallacrown complexes as building blocks was shown • Several porous complexes were characterized. Obtained compounds showed only surface sorption of N2 and H2, but they absorbed a comparatively large amount of alcohols • First compound, containing trimeric metallacrown unit is was obtained • At first time exchange parameters for GdCu5 system were calculated • The compound where hydroxamate oxygen atom acts as a bridge between MC and second building block was obtained • Studies of magnetic properties of assemblies based on the 15-MC-5 blocks with different lanthanides inside the cavity • Studies of sorption properties of assemblies based on the 15-MC-5 building blocks 19

  20. acknowledgment Sergey V. Kolotilov Matthias Zeller Allen D. Hunter Aleksey V. Shvets Laurence K. Thompson Igor O. Fritsky Anthony Addison

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