Modulation of the Structure and Photoluminescence of Bismuth(III) Chloride Hybrids by Altering the Ionic-Liquid Cations
Jiance Jin, Nan‐Nan Shen, Yang‐Peng Lin, Liao‐Kuo Gong, Hui-Ying Tong, Ke‐Zhao Du, Xiao‐Ying Huang
Abstract
Two bismuth(III) halides hybrids with room-temperature phosphorescence (RTP), namely, [BPy]2[Bi2Cl8(bpym)] (1, BPy = N-butylpyridinium) and [EPy]2[Bi2Cl8(bpym)] (2, EPy = N-ethylpyridinium), were synthesized and characterized. Structural comparison reveals that 1 and 2 possess similar anionic zigzaglike chain of [Bi2Cl8(bpym)]n2n–; however, different packing modes of anion/cations and thus different weak interactions. Interestingly, the utilization of pyridinium cations with different length of alkyl chain could tune the RTP behaviors efficiently. The RTP quantum yield (QY) is increased more than 5-fold from 1 to 2 probably due to more rigid structure of 2 arising from the additional H-bond and anion−π interactions, as confirmed by Hirshfeld surfaces analyses and PLATON calculations. Moreover, additional π–π interactions in 1 could stabilize the triplet excitons, leading to an average lifetime of 1 (11.36 ms at 77 K and 1.407 ms at 298 K) being higher than 2 (0.3618 ms at 77 K and 0.07511 ms at 298 K). Density functional theory (DFT) calculations confirm that inorganic moiety to organic ligand charge-transfer (IOCT) is involved in the phosphorescence process. The present work provides a new sight into the design of RTP metal halides through studying the structure–RTP relationship.