Optical Property Regulation through Host–Guest Interaction in a Zero-Dimensional Zr Chloride
Jiawei Lin, Xuexia Lu, Zhen Liu, Yang‐Peng Lin, Jieru Yang, Yanan Ge, Chun Zhou, Xingzhi Wang, Jinrong Li, Ke‐Zhao Du, Fei Tang, Xiao‐Ying Huang
Abstract
Halide perovskites, particularly zero-dimensional (0D) A 2 BX 6 -type structures, have garnered significant attention in diverse fields due to their exceptional photoelectric properties. This study focuses on the optical property regulation of 0D A 2 ZrCl 6 through nonprotonated cation substitution (A = [(CH 3 ) 3 SO] + and [(CH 3 ) 4 N] + ) combined with different guest ions (i.e., Sb 3+, Bi 3+, and Mn 2+ ). The varied host–guest interaction is regarded as the reason for the different luminescent behaviors. The Sb 3+ dopant has a weaker interaction with the host [(CH 3 ) 3 SO] 2 ZrCl 6 than Mn 2+ does. As a result, Sb 3+ @[(CH 3 ) 3 SO] 2 ZrCl 6 shows an excitation-dependent photoluminescence ranging from blue to orange, while Mn 2+ @[(CH 3 ) 3 SO] 2 ZrCl 6 exhibits only Mn 2+ dopant emission under different excitation wavelengths. Besides the dopant effect on the host–guest interaction, the organic cation can impact the host–guest behavior as well. [(CH 3 ) 3 SO] 2 ZrCl 6 and [(CH 3 ) 4 N] 2 ZrCl 6 have different preferences for dopant ions. Sb 3+ and Mn 2+ are favorable in the host [(CH 3 ) 3 SO] 2 ZrCl 6, while Sb 3+ and Bi 3+ are adopted in [(CH 3 ) 4 N] 2 ZrCl 6 . Due to the varied emission colors from Sb 3+ and Bi 3+ dopants, [(CH 3 ) 4 N] 2 ZrCl 6 possesses diverse photoluminescence behaviors through dopant engineering. Inside [(CH 3 ) 4 N] 2 ZrCl 6, Sb 3+ and Bi 3+ have a weak host–guest interaction, showing a varied PL from the host and guest emission centers under different excitations.