Connectivity-Dependent Conductance of 2,2'-Bipyridine-Based Metal Complexes.

The present work provides an insight into the effect of connectivity isomerization of metal-2,2'-bipyridine complexes. For that purpose, two new 2,2'-bipyridine (bpy) ligand systems, 4,4'-bis(4-(methylthio)phenyl)-2,2'-bipyridine (Lmeta) and 5,5'-bis(3,3-dimethyl-2,3-dihydrobenzothiophen-5-yl)-2,2'-bipyridine (Lpara) were synthesized and coordinated to rhenium and manganese to obtain the corresponding complexes MnLmeta(CO)3Br, ReLmeta(CO)3Br, MnLpara(CO)3Br, MoLpara(CO)4 and ReLpara(CO)3Br. The experimental and theoretical results revealed that coordination to the para system, i.e., the metal ion peripheral to the conductance path, gave a slightly increased conductance compared to the free ligand attributed to the reduced highest occupied molecular orbital (HOMO)-least unoccupied molecular orbital (LUMO) gap. The meta-based system formed a destructive quantum interference feature that reduced the conductance of a S···S contacted junction to below 10-5.5Go, reinforcing the importance of contact group connectivity for molecular wire conductance.