Bifunctional metal-organic frameworks as selective turn-on fluorescence sensors for tryptophan and heterogeneous catalysts for Knoevenagel condensation reaction

Abstract

Two new doubly interpenetrated metal-organic frameworks (MOFs) with formulas [{Zn(L1)(5-nipa)}·DMA]α (1a) and [{Cd(L2)(5-nipa)(H2O)}]α (1b) have been discussed herein, where [L1 = N,N'-(oxybis(4,1-phenylene))diisonicotinamide; L2 = N,N'-(methylenebis(4,1-phenylene)) diisonicotinamide; 5-H2nipa = 5-nitroisophthalic acid; DMA = dimethylacetamide]. A single crystal X-ray analysis reveals that 1a exhibits a 2D-interpenetrated interwoven sheet and finally adapts a 3D framework structure with the help of π···π stacking interactions. Similarly, 1b displays a two-fold interpenetrated 2D sheet-like architecture and is finally adjusted to a 3D structure. Both 1a and 1b feature channels with a cross-section of 25.06 × 25.06 Å2 and 24.01 × 24.01 Å2, respectively, running along the b-axis. Topological analysis of 1a and 1b by ToposPro suggests a (4)-connected uninodal sql topology with point symbol {44.62}. Further, 1a and 1b were exploited as molecular sensors for several amino acids exposing different shapes and sizes and exhibiting selective turn-on fluorescence sensing towards biologically important D/L-tryptophan with the notable limit of detection values of 0.084/0.110 μM and 0.143/0.141 μM, respectively, in aqueous medium. In addition, 1a and 1b were also exploited as heterogeneous catalysts towards several assorted aldehydes having different electronic environments, including sterically demanding aldehydes, under mild reaction conditions and obtained up to 97% of the respective Knoevenagel condensation product. Importantly, sterically hindered aldehydes also worked well with the MOF catalysts 1a and 1b, but showed comparatively low conversion. It is important to mention that in both cases, these MOF materials are recyclable for up to five consecutive runs without displaying any substantial loss in their sensing or catalytic activities. Moreover, the present investigation cultivates a new vision to design novel luminescent MOFs that can be used as multifunctional materials for the turn-on sensing of small organic molecules as well as instigated as heterogeneous catalysts in diverse organic transformation reactions.