| Abstract |
Three new coordination compounds, namely, a zero-dimensonal dicopper(II) complex [Cu-2(mu-MeCOO)(4)-(MeOH)(2) 1(PTA =O)(2) (1), a three-dimensional (3D) copper(II)-organic framework [Cu-3(mu-MeCOO)(6)(mu(3)-PTA=O)](n)center dot 3.5nMeCN (2), and a mixed-valence copper(I/II) one-dimensional (1D) coordination polymer [Cu-3(mu-MeCOO)(4)-(MeCOO)(mu-PTA)(2) (PTA)(n) (3), were self-assembled from copper(II) acetate and cage-like aminophosphine 1,3,5-triaza-7-phosphaadamantane (PTA) or its P-oxide (PTA=O). The obtained products were isolated as air-stable crystalline solids and characterized by IR and electron paramagnetic resonance spectroscopy, thermogravimetric and elemental analysis, as well as single crystal X-ray diffraction. Although all compounds bear dicopper(II) paddle-wheel tetraacetate [Cu-2(mu-MeCOO)(4)] blocks, they are arranged into very distinct metal-organic architectures. The structure of 2 reveals an intricate 3D metal- organic framework (MOF) driven by the mu(3)-PTA=O spacers acting in an unusual N,N,O-tridentate mode, whereas the compound 3 discloses an infinite 1D wave-like metal-organic chain with the dicopper(II) [Cu-2(mu-MeCOO)(4)] and monocopper(I) [Cu(PTA)(MeCOO)] blocks being interlinked by the mu-PTA linkers acting in an N,P-bidentate mode. Topological analysis of underlying nets was performed, revealing a decorated uninodal 3-connected framework with the the topology in 2 and a uninodal 2-connected chain with the 2C1 topology in 3. Compounds 2 and 3 broaden a still very limited family of MOFs or coordination polymers assembled from PTA or its P-oxide building blocks, also showing that PTA can be applied for the generation of unusual mixed-valence copper(I/II) derivatives. Besides, 2 represents the first example of a copper- containing 3D MOF that is driven by PTA=O or any other PTA-derived block. Magnetic properties of 1-3 were investigated, modeled, and discussed in detail, resulting in the exchange coupling parameters (J = -310, -320 cm(-1)) that indicate a strong antiferromagnetic interaction within the dicopper(II) paddle-wheel blocks. Moreover, compounds 1 and 2 show a notable catecholase activity in the aerobic oxidation of 3,5-di-tert-butyl-catechol to 3,5-di-tert-butyl-o-benzoquinone; turnover frequency values of up to 81 min(-1) were attained. |
