Year: 2025
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide The reaction between a 5,10,15,20-tetrakis(4-carboxyphenyl) porphyrin-FeCl linker (TCPP-Fe) and lanthanide ions (Ln 3+ ) in excess of l -proline coligand provides a synthetic route to two structurally different metal–organic frameworks (TCPP-FeOH 0.5 /H 2 O 0.5 )( l -proline) 2 Ln 2 (H 2 O)(DMF) 0.5 (where Ln = La 3+, Ce 3+, Pr 3+, Nd 3+, Sm 3+, and Eu 3+ ) and (TCPP-FeOH)( l -proline)Ln 1.5 (where Ln = Gd 3+, Tb 3+ Tm 3+ and Yb 3+ ). The selection between the two different structures is dependent on the lanthanide ion atomic number. From the different Ln 3+ ions used in this study, early-to-mid lanthanides, La 3+, Ce 3+, Pr 3+, Nd 3+, Sm 3+, and Eu 3+, give a structure consisting of discrete Ln 8 building units ( 1-Ln ), while mid-to-late lanthanides, Gd 3+, Tb 3+, Tm 3+, and Yb 3+, give a framework built upon one-dimensional Ln 3+ chains ( 2-Ln ). Therefore, the size of the lanthanide ion seems to play a key role in the structure selection and stability, which contrast with the commonly accepted behavior of lanthanides. Activation and subsequent argon gas sorption analyses done using 1-Nd and 2-Tb showed that 1-Nd is permanently porous with a determined surface area of 1223 ± 4 m 2 /g, while 2-Tb undergoes a structural change significantly decreasing its surface area (236 m 2 /g) from its expected value (ca. 900 m 2 /g). Stability tests on the activated samples revealed that 1-Nd lost its crystallinity after 1 month of exposure to atmospheric moisture, whereas 2-Tb retained its crystallinity, underscoring the higher long-term stability of 2-Tb compared to that of 1-Nd .
Source: Crystal Growth & Design
Institution: University of Turku
Language: English
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
Funders: Fortums Stiftelse, Neste Foundation
OpenAlex ID: W4409452265