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

• Published in: Inorganic chemistry frontiers 2018-05, Vol.5 (5), p.1162-1173
• Main Authors: Dao-Hua, Wang, Li-Ming, Zhao, Xiao-Yan, Lin, Yu-Kang, Wang, Wen-Ting, Zhang, Kai-Yue, Song, Hao-Hong, Li, Chen, Zhi-Rong
• Format: Article
• Language: English
• Subjects: Bismuth; Chains; Dimers; Erbium; Inorganic chemistry; Iodides; Lanthanum; Photoelectric effect; Photoelectric emission; Silver; Thermochromism
• ISSN: 2052-1545; 2052-1553
• DOI: 10.1039/c7qi00755h

Two new types of iodoargentate/iodobismuthate-based inorganic–organic hybrids were prepared and structurally characterized as {[Ln2(dpdo)(DMF)14](Ag12I18)}n (bpdo = 4,4′-bipyridine N,N′-dioxide, Ln = La (1), Nd (2), Sm (3)) and {[Ln(dpdo)(DMF)6](Bi2I9)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., [Ln2(dpdo)(DMF)14]6+ (dimers for 1–3) and [Ln(dpdo)(DMF)6]n3n− (1-D chains for 4–6). The (Ag12I18)n6n− chains in 1–3 are constructed from edge-sharing Ag6I12 units, and (Bi2I9)3− clusters in 4–6 are defined by two face-sharing BiI6 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.