Reactions of CuI with bis(4-phenylpyrimidine-2-thio)alkane ligands with different spacer lengths, [(phpy)(CH2)n(phpy)] (phpyH = 4-phenylpyrimidine-2-thiol; n = 1, bphpym; n = 2, bphpye; n = 3, bphpypr; n = 4, bphpyb; n = 5, bphpyp; n = 6, bphpyh), afforded a set of six [CunIn]-based coordination polymers, [{Cu(μ3-I)}2(phpym)]n (1), [{Cu(μ3-I)}4(bphpye)]n (2), [{(MeCN)Cu3(μ-I)2(μ4-I)}2(bphpypr)2]n (3), [{((MeCN)Cu)(μ-I)}2(bphpyb)]n (4), [{Cu2(μ-I)(μ3-I)}2(bphpyp)2]n (5) and [{((MeCN)Cu)(μ3-I)}2{Cu(μ-I)}2(bphpyh)2]n (6), respectively. Compounds 1–6 were characterized by elemental analysis, IR and single-crystal X-ray crystallography. 1 and 2 consist of an unique 2D network in which the 1D staircase [Cu2I2]n chains are linked by phpym or phpye ligands via the μ-η1(N)-η1(N) or μ-η1(N),η1(S)-η1(N),η1(S) coordination modes, respectively. Complexes 3 and 5 consist of double butterfly-shaped {(MeCN)Cu3(μ-I)2(μ4-I)}2 units or chair-like [Cu2(μ-I)(μ3-I)]2 units that are linked to their neighboring ones by pairs of bphpypr or bphpyp bridges to form a 1D double chain. 4 contains a 1D zigzag chain assembled by dimeric [{(MeCN)Cu}(μ-I)]2 cores and bphpyb ligands. In 6, unique 1D tandem-rhomboid [Cu2I2]n chains are connected by dphpyh ligands to form a 2D staircase network. In addition, the photoluminescent properties of 1–6 in the solid state at ambient temperature were investigated.
![Graphical abstract: Spacer length-controlled assembly of [CunIn]-based coordination polymers from CuI and bis(4-phenylpyrimidine-2-thio)alkane ligands](http://hg.y866.cn/compound/lib/scimg/usr/1/C2CE06312C.jpg)
