Semiconducting Coordination Polymers Based on the Predesigned Ternary Te-Fe-Cu Carbonyl Cluster and Conjugation-Interrupted Dipyridyl Linkers.

A series of semiconducting cluster-incorporated Cu-based coordination polymers, namely, 1D zigzag polymers [{TeFe (CO) Cu }(L)] (L=1,2-bis(4-pyridyl)ethane (bpea), 1; L=1,2-bis(4-pyridyl)ethylene (bpee), 5), 2D honeycomb-like polymers [{TeFe (CO) Cu}Cu(L) ] (L=bpea, 2; L=bpee, 6), and 2D wave-like cation-anion polymer [{Cu (L) }({TeFe (CO) Cu} (L))] (L=1,3-bis(4-pyridyl)propane (bpp), 4), as well as the macrocycle [{TeFe (CO) Cu } (bpp) ] (3) have been quantitatively synthesized via the liquid-assisted grinding from the pre-designed cluster [TeFe (CO) Cu (MeCN) ] with conjugated or conjugation-interrupted dipyridyl linkers. Notably, the most conjugation-interrupted bpp-bridged polymer 4 exhibited extraordinary semiconducting characteristics with an ultra-narrow bandgap of 1.43 eV and a DC conductivity of 1.