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note
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CX4 exists as a pentaanion at neutral pH and as a tetraanion with all phenolic hydroxy groups protonated at strongly acidic pH values, for example, at pH 2, see Ref. [12]. The formation of the ternary complexes occurs independently of this protonation equilibrium, as demonstrated by UV, NMR, and fluorescence studies at both pH 7 and pH 2 (see the Supporting Information). The crystals were also grown from acidic solution, where the CX4 tetraanion forms the corresponding ternary complex.
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18
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0343792505
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This is conceptually important, because if the guest would already form a stable transition-metal complex in the absence of host, a supramolecular self-assembly to a metalloenzyme model would no longer apply. Instead, one is dealing with host-guest complexes, in which transition-metal complexes serve as guests; the latter were previously documented, for example, for cyclodextrins; see D. R. Alston, A. M. Z. Slawin, J. F. Stoddart, D. J. Williams, Angew. Chem. 1985, 97, 771-772;
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