1,4‐Phenylenediacetate‐Based Ln MOFs – Synthesis, Structures, Luminescence, and Catalytic Activity

A series of new isostructural lanthanide MOFs, [Ln 2 (pda) 3 (H 2 O)] · 2H 2 O [Ln = La ( 1 ), Ce( 2 ), Pr( 3 ), Nd( 4 ), Sm( 5 ), Eu( 6 ), Gd( 7 ), Tb( 8 ), Dy( 9 ), Ho( 10 ), Er( 11 ), Tm( 12 ), and Yb( 13 ); H 2 dpa = 1,4‐phenylenediacetate], have been solvothermally synthesized and structurally characterized by single‐crystal (or/and powder) X‐ray diffraction analysis. All the MOFs are isostructural and consist of 1D Ln–COO helixes that are cross‐linked by the –CH 2 C 6 H 4 CH 2 – spacers of the pda 2– anions in a 3D compressed honeycomb‐shaped network with 1D open channels, which accommodate guest and coordinated water molecules. Evacuation of [Ln 2 (pda) 3 (H 2 O)] · 2H 2 O at 200 °C under vacuum generates [Ln 2 (pda) 3 ], which gives X‐ray powder diffraction patterns consistent with those of [Ln 2 (pda) 3 (H 2 O)] · 2H 2 O. MOFs 6 and 8 show characteristic luminescent properties. Activated [Tb 2 (pda) 3 ] exhibits excellent catalytic performance in the heterogeneous acetalization of benzaldehyde with methanol. The possibility for easy recycling makes this catalyst a highly promising candidate to address environmental concerns.