Reversible Multiphase Transition in a BioMOF and Its Distinctive Luminescence Turn-On in Alcohol Vapor

Abstract

Solvothermal reaction of zinc meso-tetra­(4-carboxyphenyl)­porphyrin and 2,6-diaminopurine with zinc salt in DMF affords a three-dimensional bioMOF (1-α ). Its infinite rod-shaped building block features an alternation of octahedral Zn4O and paddle-wheel Zn2 clusters bridged by 2,6-diaminopurines. The paddle-wheel Zn2 cluster undergoes reversible transformation with half into quasi-paddle-wheel Zn2 cluster and the other half into two tetrahedral mononuclear clusters upon release/uptake of guest molecules, resulting in a new phase 1-β . This single-crystal to single-crystal transformation is accompanied by luminescence on/off switching, possibly associated with the structural conversion between the porphyrin-ligand-based photoactive 1-α and the porphyrin-stacking-caused non-photoactive 1-β . Interestingly, 1-β exhibits quick luminescence turn-on in alcohol vapor instead of other volatile organic solvents by transforming into an intermediate phase 1-γ , which shows a partial luminescence enhancing likely due to the intermittent porphyrin π–π stacking. In view of experimental results and theoretical calculations, this distinctive alcohol-vapor-induced luminescence turn-on is attributed to the coordination ability to porphyrin-bound zinc ion, molecular size, and vapor pressure, in which methanol and ethanol are particularly favored.

Cooperative Catalysis of Ru(III)‐Porphyrin in CO2‐Involved Synthesis of Oxazolidinones

“…Firstly, a primary aliphatic amine reacts with CO 2 rapidly to afford the relatively stable carbamate salt intermediate ( C ‐analogue). Simultaneously, the axial‐ligand exchange in Ru III (TPP)Cl complex by 1,2‐dichloroethane leads to the formation of 1,2‐dichloroethane‐bridged Ru(III)‐porphyrin intermediate of A , with satisfied energy level because of the universally available π‐π stacking interaction between porphyrin‐rings [27–31] . Reasonably, when dichloroethane is activated by Ru‐porphyrin complex via serving as the bridge axial ligand, the two Cl−C bonds should be equally weakened without discrimination to form intermediate B upon the attack by C ‐analogue intermediate.…”

Formaldehyde recognition through aminal formation in a luminescent metal–organic framework

“…23 In our previous work, we reported a series of BioMOFs constructed with low-toxic zinc-based clusters and biomimetic units derived from nature as linkers (such as adenine and its derivatives) for luminescence sensing. 24,25 In this work, two isostructural luminescent pillar-layer MOFs (JNU-105 and JNU-105-(NH 2 ) 2 ) have been successfully synthesized via a mixed-linker strategy with a dicarboxylate (BPDC or (NH 2 The phase purities of the as-synthesized MOFs were confirmed by comparing the experiment PXRD patterns to the simulated ones from their single crystal structures (Fig. S5, ESI †).…”

“…23 In our previous work, we reported a series of BioMOFs constructed with low-toxic zinc-based clusters and biomimetic units derived from nature as linkers (such as adenine and its derivatives) for luminescence sensing. 24,25 In this work, two isostructural luminescent pillar-layer MOFs ( JNU-105 and JNU-105-(NH 2 ) 2 ) have been successfully synthesized via a mixed-linker strategy with a dicarboxylate (BPDC or (NH 2 ) 2 -BPDC, BPDC = biphenyl-4,4′-dicarboxylic acid) linker and xanthine, a natural nucleobase, as a second linker. Interestingly, JNU-105-(NH 2 ) 2 exhibits significant luminescence enhancement in the presence of HCHO, while no obvious changes in other VOCs.…”

Designing luminescent diimine-Cu(i)–phosphine complexes by tuning N-ligand and counteranions: correlation of weak interactions, luminescence and THz absorption spectra

“…10 Furthermore, complexes containing weak interactions (such as π-π, C-H⋯π and C-H⋯X (X = F, O)) widely exist in magnetic, fluorescence, biological and gel materials, [11][12][13][14][15][16] which can be used to prepare OLEDs, optical/electrical switches, and sensors. [17][18][19][20][21] These weak interactions are usually judged and characterized by the traditional X-ray single crystal diffraction method. However, for those materials that cannot produce single crystals (particularly those with large molecular weights 22 ), it is difficult to determine whether the spatial structure contains weak interactions or not.…”