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Issue 18, 2012
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Structural controls of 2D sheet copper(i) ethylene and carbonyl coordination polymers directed by anions and solvents

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Abstract

The reactions of Cu(I) ion with {BF4, ClO4, or PF6} anions and 6,6′-dimethyl-4,4′-bipyrimidine (Me2bpm) under C2H4 or CO in MeOH preferentially afforded three 2D sheet Cu(I)–Me2bpm/{C2H4, CO} adducts [Cu4(Me2bpm)3(C2H4)3(MeCN)](BF4)4·0.33MeOH}n (2), {[Cu4(Me2bpm)3-(C2H4)3(MeOH)0.33](ClO4)4}n (3), and {[Cu4(Me2bpm)3(CO)3(MeCN)](PF6)4·0.33MeCN}n (4), whereas the similar reaction of Cu(I) ion with a BF4 anion and Me2bpm under CO in MeOH gave the metallamacrocyclic tetranuclear Cu(I)–Me2bpm/CO adduct [Cu4(Me2bpm)4(CO)4]-(BF4)4·4MeOH (5). In Cu(I)–Me2bpm/{C2H4, CO} adducts 2–4, it should be noted that the metallacalix[3]arene structures of the [Cu3(Me2bpm)3]3+ framework are linked through another Cu atom with MeCN (2 and 4) or MeOH (3) to produce a chiral 2D sheet structure with small Cu3 and large Cu9 cavities. In the small triangular Cu3 cavities, one MeOH (2) or MeCN (4) molecule is encapsulated in complexes 2 and 4, whereas these Cu3 cavities are empty in complex 3. In the large Cu9 cavities, one anion (X = BF4 (2), ClO4 (3) or PF6 (4)) is surrounding by six Me groups of three Me2bpm on the upside and three anions (X) are functionally accommodated on the downside for complexes 2–4, respectively. In the Cu(I)–Me2bpm/CO adduct 5, two of the four BF4 anions are accommodated in the upper and lower cavities of the [Cu4(Me2bpm)4] framework. We demonstrated that the metallamacrocyclic and polymeric 2D sheet Cu(I)–Me2bpm/{C2H4, CO} adducts can be reasonably self-assembled under the direction of anions and solvents.

Graphical abstract: Structural controls of 2D sheet copper(i) ethylene and carbonyl coordination polymers directed by anions and solvents

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Publication details

The article was received on 14 Feb 2012, accepted on 06 Jun 2012 and first published on 07 Jun 2012


Article type: Paper
DOI: 10.1039/C2CE25211B
CrystEngComm, 2012,14, 5955-5962

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    Structural controls of 2D sheet copper(I) ethylene and carbonyl coordination polymers directed by anions and solvents

    M. Maekawa, T. Tominaga, K. Sugimoto, T. Okubo, T. Kuroda–Sowa, M. Munakata and S. Kitagawa, CrystEngComm, 2012, 14, 5955
    DOI: 10.1039/C2CE25211B

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