Citation: Yujing HUANG, Yuan GOU, Kexin JI, Xingcai HUANG, Siyuan CHEN, Jiaojiao KONG, Yanqing WANG. Thiazolo[5,4-d]thiazole fluorophore functionalization in 2D Cd(Ⅱ) metal-organic frameworks triggering a luminescence enhancement for highly sensitive aqueous antibiotic sensing[J]. Chinese Journal of Inorganic Chemistry, ;2026, 42(9): 1945-1958. doi: 10.11862/CJIC.20260147 shu

Thiazolo[5,4-d]thiazole fluorophore functionalization in 2D Cd(Ⅱ) metal-organic frameworks triggering a luminescence enhancement for highly sensitive aqueous antibiotic sensing

School of Chemistry and Environmental Engineering, Yancheng Teachers University, Yancheng, Jiangsu 224007, China

Corresponding author: Xingcai HUANG, huangxc82@126.com; huangxc@yctu.edu.cn Yanqing WANG, wangyanqing@yctu.edu.cn
Received Date: 29 April 2026
Revised Date: 2 August 2026

Figures(8)

To overcome the non-radiative energy dissipation that weakens the intrinsic emission of metal-organic frameworks (MOFs), a fluorophore functionalization strategy was applied to restrict intramolecular ligand motion and to enhance the photoluminescence. Two analogous frameworks were synthesized and systematically compared: {[Cd(4bpyttz)(CDA)]·2DMF}_n (MOF 1), constructed from a ligand with a rigidly fused thiazolo[5,4-d]thiazole (TTZ) core, and [Cd(4bbpy)(CDA)]_n (MOF 2), which incorporates a freely rotatable phenyl core (4bpyttz=2,5-bis(pyridin-4-yl)thiazolo[5,4-d]thiazole, 4bbpy=1,4-bis(pyridin-4-yl)benzene, H₂CDA=4,4′-carbonyldibenzoic acid). Photophysical and density functional theory (DFT) studies reveal that the TTZ core localizes both the HOMO and LUMO on itself, thereby deactivating the ligand-to-ligand charge transfer (LLCT) pathway present in MOF 1. This core rigidification enforces ordered π…π stacking and suppresses non-radiative decay, leading to dramatically enhanced solid-state photoluminescence. Consequently, MOF 1 functions as a highly selective turn-off fluorescent sensor for nitrofuran antibiotics in aqueous media, achieving limits of detection of 1.59 μmol·L^-1 for nitrofurazone (NZF) and 2.77 μmol·L^-1 for nitrofurantoin (NFT). Mechanistic studies show that this rapid quenching is primarily governed by the inner filter effect (IFE) coupled with photoinduced electron transfer (PET).
- metal-organic frameworks,
- thiazolo[5,4-d]thiazole,
- fluorophore functionalization,
- fluorescent sensing,
- nitrofuran antibiotics
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