Photochromic and Room Temperature Phosphorescent Donor-Acceptor Hybrid Crystals Regulated by Core-Substituted Naphthalenediimides

Yi-Ming Di; Meng-Hua Li; Ming-Hua You; Shu-Quan Zhang; Mei-Jin Lin

doi:10.1021/acs.inorgchem.1c02020

Photochromic and Room Temperature Phosphorescent Donor-Acceptor Hybrid Crystals Regulated by Core-Substituted Naphthalenediimides

Inorg Chem. 2021 Nov 1;60(21):16233-16240. doi: 10.1021/acs.inorgchem.1c02020. Epub 2021 Oct 14.

Authors

Yi-Ming Di¹, Meng-Hua Li¹, Ming-Hua You², Shu-Quan Zhang³, Mei-Jin Lin^{1

4}

Affiliations

¹ Key Laboratory of Molecule Synthesis and Function Discovery (Fujian Province University), College of Chemistry, Fuzhou University, Fuzhou 350108, China.
² College of Materials Science and Engineering, Fujian University of Technology, Fuzhou 350118, China.
³ College of Zhicheng, Fuzhou University, Fuzhou 350002, China.
⁴ College of Materials Science and Engineering, Fuzhou University, Fuzhou 350116, China.

PMID: 34648276
DOI: 10.1021/acs.inorgchem.1c02020

Abstract

Donor-acceptor (D-A) hybrid crystals are an emerging kind of crystalline hybrid material composed of semiconductive inorganic donors and organic acceptors. Except for the intrinsic photochromism, recently we have reported that the anion-π polyoxometalate (POM)/naphthalenediimide (NDI) hybrid crystals could produce an interesting room temperature phosphorescence (RTP) quantum yield up to 7.2%. Herein, we extended into core-substituted NDIs and anticipated the regulation of their photochromic and RTP properties. Thus, two hybrid crystals, namely (H₄BDMPy-Br₂NDI)·(NMP)₄·(HPW₁₂O₄₀) (1) and (H₄BDMPy-I₂NDI)·(HPW₁₂O₄₀) (2) (H₂BDMPy-Br₂NDI: N,N'-bis(3,5-dimethylpyrazolyl)-2,6-dibromo-1,4,5,8-naphthalenediimide and H₂BDMPy-I₂NDI: N,N'-bis(3,5-dimethylpyrazolyl)-2,6-diiodide-1,4,5,8-naphthalenediimide), have been synthesized from phosphotungstic anions (PW₁₂O₄₀^3-) and Br or I core-substituted NDIs. Compared to the core-unsubstituted analogues (H₄BDMPy-NDI)·(NMP)₄·(HPW₁₂O₄₀) (3), 2 with photosensitive iodine substituents is more sensitive to light, which can become discolored under natural light. As a result of the heavy-atom effect, hybrid 1 exhibits remarkable RTP with the quantum yield up to 10.2% and a lifetime of 1.14 ms.