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

2.  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.  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 3 9-MC-3 12-MC-4 15-MC-5 Metallacrowns (MC) are polynuclear assemblies, which are usually obtained on the basis hydroxamic acids

4. 4 Building block 1 [Cu 5 L 4 ] 2+ : 12-MC-4 Building block 2 [LnCu 5 (L 1 ) 5 ] 3+ : 15-MC-5 (Ln 3+ = Sm 3+, Eu 3+, Gd 3+, Nd 3+, Pr 3+, Ho 3+, Dy 3+ ) The distance between mean planes LnCu 5 of two neighbouring MC units is ~6Å [Cu 5 (ahpha) 4 ](ClO 4 ) 2 [GdCu 5 (GlyHA) 5 ] 2 (SO 4 ) 3

5.  polycarboxylates  anionic mononuclear complexes K 3 Cr(C 2 O 4 ) 3 K 2 Cu(C 2 O 4 ) 2 5 and others

6. + DMF/ H 2 O DMF/ MeOH 6 Complex 1aComplex 1 π-π stacking: 3.279(4)Å. Selected hydrogen bonds O14-H8D = 1.941(2) Å, O15-H11D = 2.035(4) Å Cu3 - O10’ 2.894(5)Å Cu3 – O9’ 2.988(3)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 base

7. Volume of the voids: 396.7Å 3 or 20.6%, which corresponds to 0.085 cm 3 /g voids along axis a 16.5  6.1 Å Complex 1 Complex 1a Volume of the voids is 1879.1 Å 3 or 18.7% which corresponds to 0.073 cm 3 /g 7 All void volumes calculated by Platon for probe molecule with r = 1.4 Å assuming that the structure is retained after desolvatation voids along axis b 12.3  6.6 Å

8. 8 + DMF/H 2 O Volume of the voids is 441.3Å 3 or 11.8% (Platon calculations), which corresponds to 0.049 cm 3 /g Complex 2 [Cu 5 (ahpha) 4 (p-C 8 H 4 O 4 ). 2H 2 O] 2 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) base

9. + DMF/MeOHDMF/Et 2 O 9 Complex 3 Complex 3a Voids 10x11 Å. Volume of the voids is 5411.9 Å 3 or 40.7% (Platon calculations), which corresponds to 0.243 cm 3 /g NONPOROUS Two deprotonated maleic acids are bounded to one metallacrown unit Cu3-O8 = 2.574(2) 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

10. 10 DMF/H 2 O + Complex 4 Channels 9  12 Å. According to the Platon calculations pore volume is 3343.35(4)Å 3 or 26.6 %, which corresponds to 0.129 cm 3 /g This complex is the first example of metallacrown trimerization

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

12. J2 Cu3 Cu4 Cu5 Cu2 J2 J1 Cu1 J1 J2 J1 12 χ M T vs. T plot for complexes 1 (□) and 2: (○) χ M T vs. T plot for complex 4 g Cr = 1.959 (fixed)

13. + DMF/H 2 O 13 Two isomers of coordination polymer were isolated from the reaction mixture Complex 5 Complex 5a 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

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

15. Cu3 Cu4 Gd Cu2 Cu1 J1 J2 Cu5 J1 J2 J 1 =-61.0 cm -1, J 2 = +0.6 cm -1, zJ=-0.035 cm -1, g Gd =2.033, g Cu =2.1, TIP=0.0011, R 2 = 3.01. 10 -5 This complex is the first example of 15-MC-5 systems, for which exchange parameters are reported χ M T vs. T plot for complex 6 Distance between mean planes GdCu 5 of two neighbouring MC units is about 7.5 Å. 15

16. DMF/H 2 O + K 3 Cr(C 2 O 4 ) 3 16 Volume of the voids is 4884.2 Å 3 or 19.8 % (Platon calculations) which corresponds to 0.074 cm 3 /g Voids along axis c 5.6x9.9 Å Complex 7 Complex 7 is 1D zig-zag coordination polymer, which chains are packed into the 2D net due to the large system of hydrogen bonds

17. J 1 =-25.0 сm -1, J 2 = +1.0 cm -1, J Cu-Cr = -12.0 cm -1, J Gd-Cr = +0.5 cm -1 zJ=-0.009 сm -1, g Gd =2.033 (fixed), g Cu =2.1 (fixed), g Cr =1.959 (fixed), TIP=0.0019, R 2 = 3.86. 10 -5 Cu3 Cu4 Gd Cu2 Cu1 J1 J2 Cu5 J1 J2 17 Average distance Cu – Cu is 4.571Å, while Cu-Gd = 3.878 Å Contacts: Cu – Cr is 5.432 Å, while Gd-Cr = 5.952 Å

18. DMF/H 2 O + K 2 Cu(C 2 O 4 ) 2 18 Complex 8 Complex 8 is 2D coordination polymer Volume of the voids is 2139.3 Å 3 or 12.5 % (Platon calculations), which corresponds to 0.055 cm 3 /g Average distances inside MC unit Cu – Cu is 4.559Å, while Cu-Gd = 3.915 Å Average distances outside MC unit Cu – Cu is 3779Å, while Cu-Gd = 5.736 Å Voids along axis a 6.6x9.67 Å

19. 19 The possibility of using metallacrown complexes as building blocks was shown Several porous complexes were characterized. Obtained compounds showed only surface sorption of N 2 and H 2, but they absorbed a comparatively large amount of alcohols First compound, containing trimeric metallacrown unit is was obtained At first time exchange parameters for GdCu 5 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

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