A novel MOF of Zn-APT can be used as the fluorescence probe to detect Fe 3+ in aqueous solution with the high sensitivity and selectivity. It can absorb hemoporphyrin dihydrochloride on its surface to form red crystal Zn-APT-PH, which can also be used as the fluorescence probe to detect Fe 2+ in aqueous solution with the high sensitivity and selectivity. • A fluorescence metal–organic framework of Zn-APT was synthesized. • Zn-APT has the novel and compact structure with a nbo topology type. • Zn-APT can be used as a fluorescent probe to detect Fe 3+ effectively. • Zn-APT can adsorb hemoporphyrin dihydrochloride to form a red-brown crystal Zn-APT-PH. • Zn-APT-PH can be used as a fluorescent probe to detect Fe 2+ effectively. A fluorescence metal-organic framework [Zn 3 (APT) 4 ]·2H 2 O (Zn-APT) was synthesized from Zn(NO 3 ) 2 ·6H 2 O and 2-amino-6-purinethiol (ATP) by the solvothermal reaction. Zn-APT has a novel compact structure with a nbo topology type. The analyses of single-crystal diffraction reveal that Zn-APT crystallizes in a cubic crystal system and F d 3 ¯ c space group. Based on a large amount of π-conjugated organic ligands of ATP and d 10 metal center of Zn 2+ , Zn-APT can emit strong luminescence. It can be used as a fluorescent probe to detect Fe 3+ ion effectively. The detection limit is 0.28 μM and K sv (quenching efficiency) is 2.1 × 10 4 M −1 . In addition, Zn-APT can adsorb hemoporphyrin dihydrochloride to produce a red-brown crystal Zn-APT-PH. Interestingly, it can also be used to detect Fe 2+ ion efficiently with the detection limit of 0.12 μM and K sv of 1.9 × 10 4 M −1 .