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

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.