Photochromic Semiconductors: Bottom-Up Strategy to Construct Type II-Stacking Viologen π-Aggregates

Peng-Hao Wang; Bin-Wen Liu; Guo-Qiang Wang; Cai Sun

doi:10.1021/acs.inorgchem.2c02760

Photochromic Semiconductors: Bottom-Up Strategy to Construct Type II-Stacking Viologen π-Aggregates

Inorg Chem. 2022 Oct 31;61(43):17196-17201. doi: 10.1021/acs.inorgchem.2c02760. Epub 2022 Oct 20.

Authors

Peng-Hao Wang¹, Bin-Wen Liu^{2

3}, Guo-Qiang Wang⁴, Cai Sun^{1

2}

Affiliations

¹ College of Chemistry, Fuzhou University, Fuzhou, Fujian 350108, China.
² State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350608, China.
³ Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou, Fujian 350108, China.
⁴ College of Materials Science and Engineering, Fuzhou University, Fuzhou, Fujian 350108, China.

PMID: 36265225
DOI: 10.1021/acs.inorgchem.2c02760

Abstract

Semiconductor conductivities depend largely on the crystal structures and the associated electronic structures. If the electronic structures can be switched reversibly in the same crystal structure, then a drastic conductivity change may be controllable. The effect of electron transfer (ET) on semiconductor conductivity remained elusive so far. In this work, a series of two pillared inorganicorganic hybrid photochromic semiconductors (PSCs), [(CQ)Pb₃X₆(H₂O)]·2H₂O [X = Cl (1) and Br (2), CQ = N-4,4'-bipyridiniopropionate (viologen)], with II-stacking viologen π-aggregates, are constructed by a bottom-up self-assembly strategy through inorganic skeleton-directed intercalation and intermolecular noncovalent interaction. The conductivities are abnormally "invariant" after photoinduced ET, breaking the convention that the generation of radicals favors conductivity. The abnormally "invariant" conductivities are mainly derived from approximate electronic couplings before and after ET between II-stacking viologen π-aggregates.