Unique Copper–Organic Networks Self-Assembled from 1,3,5-Triaza-7-Phosphaadamantane and Its Oxide: Synthesis, Structural Features, and Magnetic and Catalytic Properties

Three new coordination compounds, namely, a zero-dimensonal dicopper­(II) complex [Cu₂(μ-MeCOO)₄­(MeOH)₂]­(PTA = O)₂ (<b>1</b>), a three-dimensional (3D) copper­(II)-organic framework [Cu₃(μ-MeCOO)₆­(μ₃-PTAO)]_<i>n</i>­·3.5<i>n</i>MeCN (<b>2</b>), and a mixed-valence copper­(I/II) one-dimensional (1D) coordination polymer [Cu₃(μ-MeCOO)₄­(MeCOO)­(μ-PTA)₂­(PTA)]_<i>n</i> (<b>3</b>), 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 [Cu₂(μ-MeCOO)₄] blocks, they are arranged into very distinct metal–organic architectures. The structure of <b>2</b> reveals an intricate 3D metal–organic framework (MOF) driven by the μ₃-PTAO spacers acting in an unusual N,N,O-tridentate mode, whereas the compound <b>3</b> discloses an infinite 1D wave-like metal–organic chain with the dicopper­(II) [Cu₂(μ-MeCOO)₄] and monocopper­(I) [Cu­(PTA)­(MeCOO)] blocks being interlinked by the μ-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 <b>ths</b> topology in <b>2</b> and a uninodal 2-connected chain with the <b>2C1</b> topology in <b>3</b>. Compounds <b>2</b> and <b>3</b> 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, <b>2</b> 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 <b>1</b>–<b>3</b> were investigated, modeled, and discussed in detail, resulting in the exchange coupling parameters (<i>J</i> = −310, −320 cm^–1) that indicate a strong antiferromagnetic interaction within the dicopper­(II) paddle-wheel blocks. Moreover, compounds <b>1</b> and <b>2</b> show a notable catecholase activity in the aerobic oxidation of 3,5-di-<i>tert</i>-butyl-catechol to 3,5-di-<i>tert</i>-butyl-<i>o</i>-benzoquinone; turnover frequency values of up to 81 min^–1 were attained