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Structure‐Directing Forces in Intercluster Compounds of Cationic [Ag 14 (CC t Bu) 12 Cl] + Building Blocks and Polyoxometalates: Long‐Range versus Short‐Range Bonding Interactions
Author(s) -
Gruber Franziska,
SchulzDobrick Martin,
Jansen Martin
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200902538
Subject(s) - polyoxometalate , cationic polymerization , chemistry , crystallography , crystallization , stereochemistry , medicinal chemistry , catalysis , polymer chemistry , organic chemistry
Crystallization of [Ag 14 (CC t Bu) 12 Cl][BF 4 ] and different polyoxometalates in organic solvents yields a series of new intercluster compounds: [Ag 14 (CC t Bu) 12 Cl(CH 3 CN)] 2 [W 6 O 19 ] ( 1 ), ( n Bu 4 N)[Ag 14 (CC t Bu) 12 Cl(CH 3 CN)] 2 [PW 12 O 40 ] ( 2 ), and [Ag 14 (CC t Bu) 12 Cl] 2 [Ag 14 (CC t Bu) 12 Cl(CH 3 CN)] 2 [SiMo 12 O 40 ] ( 3 ). Applying the same technique to a system starting from polymeric {[Ag 3 (CC t Bu) 2 ][BF 4 ]⋅0.6 H 2 O} n and the polyoxometalate ( n Bu 4 N) 2 [W 6 O 19 ] results in the formation of [Ag 14 (CC t Bu) 12 (CH 3 CN) 2 ][W 6 O 19 ] ( 4 ). Here, the Ag 14 cluster is generated from polymeric {[Ag 3 (CC t Bu) 2 ][BF 4 ]⋅0.6 H 2 O} n during crystallization. In a similar way, [Ag 15 (CC t Bu) 12 (CH 3 CN) 5 ][PW 12 O 40 ] ( 5 ) has been obtained from {[Ag 3 (CC t Bu) 2 ][BF 4 ]⋅0.6 H 2 O} n and ( n Bu 4 N) 3 [PW 12 O 40 ]. The use of charged building blocks was intentional, because at these conditions the contribution of long‐range Coulomb interactions would benefit most from full periodicity of the intercluster compound, thus favoring formation of well‐crystalline materials. The latter has been achieved, indeed. However, as a most conspicuous feature, equally charged species aggregate, which demonstrates that the short‐range interactions between the “surfaces” of the clusters represent the more powerful structure direction forces than the long‐range Coulomb bonding. This observation is of significant importance for understanding the mechanisms underlying self‐organization of monodisperse and structurally well‐defined particles of nanometer size.