Iodoargentate/iodobismuthate-based materials hybridized with lanthanide-containing metalloviologens: thermochromic behaviors and photocurrent responses

Two new types of iodoargentate/iodobismuthate-based inorganic–organic hybrids were prepared and structurally characterized as {[Ln 2 (dpdo)(DMF) 14 ](Ag 12 I 18 )} n (bpdo = 4,4′-bipyridine N , N ′-dioxide, Ln = La ( 1 ), Nd ( 2 ), Sm ( 3 )) and {[Ln(dpdo)(DMF) 6 ](Bi 2 I 9 ) 2 } n (Ln = La ( 4 ), Pr ( 5 ), Er ( 6 )). These lanthanide–silver/bismuth heterometallic hybrids feature the novel templates of lanthanide-containing metalloviologen analogs, i.e. , [Ln 2 (dpdo)(DMF) 14 ] 6+ (dimers for 1–3 ) and [Ln(dpdo)(DMF) 6 ] n 3n− (1-D chains for 4–6 ). The (Ag 12 I 18 ) n 6n− chains in 1–3 are constructed from edge-sharing Ag 6 I 12 units, and (Bi 2 I 9 ) 3− clusters in 4–6 are defined by two face-sharing BiI 6 otcahedra. The versatile weak interactions between metalloviologens and metal iodides stabilize the structures. Upon the introduction of metalloviologens, reversible thermochromism can be found in 1–6 . Besides, electrodes with films of 1–6 exhibit effective and repeatable photocurrent responses. Finally, the possible thermochromism and photocurrent response mechanisms are also discussed.