A highly sensitive turn-on ratiometric luminescent probe based on postsynthetic modification of Tb3+@Cu-MOF for H2S detection†
Abstract
The fabrication of luminescent materials with lanthanide cations encapsulated within MOF pores is currently of interest because luminescent materials are used in numerous applications. In this study, a distinctive strategy via postsynthetic modification (PSM) of a novel metal–organic framework [Cu(HCPOC)2]n (Cu1) (H2CPOC = 5-(4′-carboxyphenoxy)nicotinic acid) and terbium ions (Tb3+) for sensing hydrogen sulfide (H2S) is reported. The obtained composite Tb3+@Cu1 emits a weak typical Tb3+ ion emission and strong ligand-centred emission. Interestingly, H2S, as a strong electron donor, can strongly enhance the luminescence of Tb3+ through its superior affinity for Cu2+ ions. The composite Tb3+@Cu1 was designed as a luminescent turn-on ratiometric probe for H2S detection, showing high sensitivity and selectivity. The detection limit of Tb3+@Cu1 (1.20 μM) is far below that of Cu1 (13.25 μM). Moreover, a similar ligand, 5-(4′-carboxyphenyl)nicotinic acid (H2CPC), was used to synthesize a fascinating structure, [Cu5(CPC)2(HCPC)2(OH−)4]n (Cu2), which was quite similar to that of the famous semiconductor MoS2, with the advantageous support of an organic linker between layers, and it showed a band gap of 2.45 eV.