Cross-linking nanostructured spherical capsules as building units by crystal engineering: related chemistry

The compound [Mo72Fe30O252(CH3COO)(10){Mo2O7(H2O)} {H2Mo2O8(H2O)}(3) (H2O)( 91)].ca. 140 H2O 3 = 3a.ca. 140 H2O an important educt for an unusual solid state reaction, can now be obtained easily by reacting (NH4)(42)[{(Mo2O4)- O-V(CH3COO)}(30){(Mo)Mo5O21(H2O)(6)}(12)].10 CH3COONH4.ca. 300 H2O 1 with F eCl3.6 H2O in water. Interestingly, the freshly precipitated crystals of 3 contain discrete spherical clusters of the type {(Mo72Fe30III)-Fe-VI} with as yet unprecedented 30 x 5 unpaired electrons (S = 150/2 at room temperatu re). Upon drying 3, its cluster units 3a get covalently linked to form laye rs in a step by step solid state reaction, according to the scheme describe d below, resulting finally in the crystalline reaction product [H4Mo72Fe30O 254(CH3COO)(10){Mo2O7(H2O)} {H2Mo2O8(H2O)}(3)(H2O)(87)].ca. 80 H2O 4=4a.ca. 80 H2O. The linking process at the Fe sites follows the well known inorgan ic condensation process leading to Fe-III polycations in actueous solution according to the scheme Fe(OH2)+ (H2O)Fe->(-H+) Fe(OH)+ (H2O)Fe ->(-H+/-H2O ) Fe-O-Fe and thus is based on a type of crystal engineering with nanostruc tured spherical building blocks. This process does not allow chaotic charac teristics in contrast to the mentioned polycation formation. Careful invest igation leads to the identification of an intermediate 5 containing cluster s 5a - with the same cluster composition as 3a and 4a - in the closest poss ible non-covalent contact. The related materials are of tremendous interest for magnetochemistry (nano-magnet-technology). [3] -> (-crystal water) [5] -> (deprotonation and condensation) [4] (C) 2000 Editions scientifiques et mCdicales EIsevier SAS. All rights reserved.