An unprecedented 2-D cluster polymer constructed from unique mixed-valence Cu~I_6Cu~(II)_6 subunits

摘要

A new 2-D cluster-based polymer {[Cu~I_6Cu ~(II)_6L_6(H_2O)_3(CH _3OH)_6]·5H_2O·3CH _3OH}_n (2) (H_3L = C_6H _5C(O)NHC(S)NHCH_2COOH) containing unique mixed-valence [Cu~I_6Cu~(II)_6L_6] subunits was synthesized by reaction of single crystals of [Ln_2(H _2L)_4(Phen)_2(NO_3)_2] (Ln = Pr (1a), Nd (1b) or Ho (1c)) (Phen = 1,10-phenanthroline) with copper(ii) acetate in aqueous DMF. Interestingly, cation-exchanged products {[Cu ~I_6Cu~(II)_5Zn(H_2O) _3(CH_3OH)_6]·5H_2O· 3CH_3OH}_n (3) or {[Cu~I_6Cu ~(II)_4Co_2(H_2O)_3(CH _3OH)6_]·5H_2O·3CH _3OH}n (4) were obtained from single crystals of 2 and the appropriate M(NO_3)_2 (M = Zn or Co) in H_2O.