Download presentation

Presentation is loading. Please wait.

Published byGuy Brunning Modified about 1 year ago

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 cm 3 /g voids along axis a 16.5 6.1 Å Complex 1 Complex 1a Volume of the voids is Å 3 or 18.7% which corresponds to 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 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 Å 3 or 40.7% (Platon calculations), which corresponds to 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 (4)Å 3 or 26.6 %, which corresponds to 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 = (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 = 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= cm -1, g Gd =2.033, g Cu =2.1, TIP=0.0011, R 2 = 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 Å 3 or 19.8 % (Platon calculations) which corresponds to 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 = cm -1, J Gd-Cr = +0.5 cm -1 zJ= сm -1, g Gd =2.033 (fixed), g Cu =2.1 (fixed), g Cr =1.959 (fixed), TIP=0.0019, R 2 = Cu3 Cu4 Gd Cu2 Cu1 J1 J2 Cu5 J1 J2 17 Average distance Cu – Cu is 4.571Å, while Cu-Gd = Å Contacts: Cu – Cr is Å, while Gd-Cr = 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 Å 3 or 12.5 % (Platon calculations), which corresponds to cm 3 /g Average distances inside MC unit Cu – Cu is 4.559Å, while Cu-Gd = Å Average distances outside MC unit Cu – Cu is 3779Å, while Cu-Gd = 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

Similar presentations

© 2017 SlidePlayer.com Inc.

All rights reserved.

Ads by Google