Assembly of [CunIn]-based coordination polymers from cracking the 3D framework of bulk CuI via flexible N-heterocyclic ligands.

Solvothermal reactions of CuI with four flexible N-heterocyclic ligands, 1,2-bis(4-pyridyl)ethane (bpe), 1,1'-(1,4-butanediyl)bis-1H-benzimidazole (bbbm), 1,1'-(1,4-butanediyl)bis-1H-benzotriazole (bbbt), and 1,1'-(1,5-pentanediyl)bis-1H-benzimidazole (pbbm), afforded four new [Cu(n)I(n)]-based coordination polymers, [Cu3I(mu-I)(mu3-I)(bpe)3]n (1), {[CuI(bbbm)1.5].0.25MeCN}n (2), and [Cu4(mu3-I)4L2]n (3: L = bbbt; 4: L = pbbm), respectively. Compounds 1-4 were characterized by elemental analysis, IR and X-ray crystallography. 1 consists of an unique 2D network in which 1D [CuI(bpe)]n zigzag chains are embroidered alternatively onto the two faces of a 2D [Cu4(mu-I)2(mu3-I)2(bpe)2]n layer through pairs of bpe bridges. 2 contains a 66-membered metallomacrocyclic [CuI(bbbm)1.5]6 unit that fuses with its neighbouring ones via sharing Cu atoms to form a 2D (6,3) layer network. 3 or 4 contains a cubanelike [Cu4(mu3-I)4] core, which works as a cross-shaped four-connecting node to link its four equivalent units to form a 2D (4,4) cross-shaped network () or acts as a Y-shaped three-connecting node to connect its three equivalent ones to form a 1D double chain (). In addition, the photoluminescent properties of in solid state at ambient temperature were also investigated.