Structure and photoluminescence tuning features of Mn(2+)- and Ln(3+)-activated Zn-based heterometal-organic frameworks (MOFs) with a single 5-methylisophthalic acid ligand

In attempts to investigate whether the photoluminescence properties of the Zn-based heterometal-organic frameworks (MOFs) could be tuned by doping different Ln(3+) (Ln = Sm, Eu, Tb) and Mn(2+) ions, seven novel 3D homo- and hetero-MOFs with a rich variety of network topologies, namely, [Zn(mip)](n) (Zn-Zn), [Zn(2)Mn(OH)(2)(mip)(2)](n) (Zn-Mn), [Mn(2)Mn(OH)(2)(mip)(2)](n) (Mn-Mn), [ZnSm(OH)(mip)(2)](n) (Zn-Sm), [ZnEu(OH)(mip)(2)](n) (Zn-Eu1), [Zn(5)Eu(OH)(H(2)O)(3)(mip)(6)·(H(2)O)](n) (Zn-Eu2), and [Zn(5)Tb(OH)(H(2)O)(3)(mip)(6)](n) (Zn-Tb), (mip = 5-methylisophthalate dianion), have been synthesized hydrothermally based on a single 5-methylisophthalic acid ligand. All compounds are fully structurally characterized by elemental analysis, FT-IR spectroscopy, TG-DTA analysis, single-crystal X-ray diffraction, and X-ray powder diffraction (XRPD) techniques. The various connectivity modes of the mip linkers generate four types of different structures. Type I (Zn-Zn) is a 3D homo-MOF with helical channels composed of Zn(2)(COO)(4) SBUs (second building units). Type II (Zn-Mn and Mn-Mn) displays a nest-like 3D homo- or hetero-MOF featuring window-shaped helical channels composed of Zn(4)Mn(2)(OH)(4)(COO)(8) or Mn(4)Mn(2)(OH)(4)(COO)(8) SBUs. Type III (Zn-Sm and Zn-Eu1) presents a complicated corbeil-like 3D hetero-MOF with irregular helical channels composed of (SmZnO)(2)(COO)(8) or (EuZnO)(2)(COO)(8) heterometallic SBUs. Type IV (Zn-Eu2 and Zn-Tb) contains a heterometallic SBU Zn(5)Eu(OH)(COO)(12) or Zn(5)Tb(OH)(COO)(12), which results in a 3D hetero-MOF featuring irregular channels impregnated by parts of the free and coordinated water molecules. Photoluminescence properties indicate that all of the compounds exhibit photoluminescence in the solid state at room temperature. Compared with a broad emission band at ca. 475 nm (λ(ex) = 380 nm) for Zn-Zn, compound Zn-Mn exhibits a remarkably intense emission band centered at 737 nm (λ(ex) = 320 nm) due to the characteristic emission of Mn(2+). In addition, the fluorescence intensity of compound Zn-Mn is stronger than that of Mn-Mn as a result of Zn(2+) behaving as an activator for the Mn(2+) emission. Compound Zn-Sm displays a typical Sm(3+) emission spectrum, and the peak at 596 nm is the strongest one (λ(ex) = 310 nm). Both Zn-Eu1 and Zn-Eu2 give the characteristic emission transitions of the Eu(3+) ions (λ(ex) = 310 nm). Thanks to the ambient different crystal-field strengths, crystal field symmetries, and coordi