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Chapter 4 63<br />
compared with the parent material, the actual compositions of these Ru-DEMOFs are very<br />
difficult to establish and are not entirely clear. This stems from the structural complexity<br />
of such multi‐component solid solution MOFs and a range of possible compositional<br />
variations, which are not mutually exclusive (counter-ions, residual synthesis<br />
components such as linkers, coordination modulators etc.).<br />
Figure 4.5 Design concept of the DEMOFs applying the mixed component/fragmented linker solid<br />
solution approach and sketch of the two possible, most important paddlewheel-node related<br />
defects.<br />
Figure 4.5 summarizes the concept of defects introduction into mixed-valence<br />
[M3(BTC)2Yy]n by using divalent isophthalate linkers as fragmented variants of trivalent<br />
BTC. Mainly, two types of defects need to be distinguished: Type A refers to structurally<br />
and electronically modified paddlewheel units (missing one carboxylate ligator function),<br />
in which (at least) one out of the four bridging carboxyl groups from the parent BTC linker<br />
in the regular paddlewheels has been partly substituted by the (neutral) functional group<br />
of the DL. Consequently, for charge compensation, the metal sites could be either partly<br />
reduced (mixed-valence state) or may carry additional anionic (mono-valent) ligands<br />
(Y) [137-138] However, apart from such type A, defects of type B could be formed, where<br />
whole paddlewheel nodes are eliminated from the structure, as it has been demonstrated
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