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Unique copper–organic networks self-assembled from 1,3,5-triaza-7-phosphaadamantane and its oxide : synthesis, structural features, and magnetic and catalytic properties.
Autorzy
Rok wydania
2018
Czasopismo
Numer woluminu
18
Strony
2814-2823
DOI
10.1021/acs.cgd.7b01581
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
Three new coordination compounds, namely, a zero-dimensonal dicopper(II) complex [Cu2(μ-MeCOO)4(MeOH)2](PTA = O)2 (1), a three-dimensional (3D) copper(II)-organic framework [Cu3(μ-MeCOO)6(μ3-PTA═O)]n·3.5nMeCN (2), and a mixed-valence copper(I/II) one-dimensional (1D) coordination polymer [Cu3(μ-MeCOO)4(MeCOO)(μ-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 [Cu2(μ-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 μ3-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) [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 ths 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.
Adres publiczny
https://doi.org/10.1021/acs.cgd.7b01581
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