Confinement Effects of Metal–Organic Framework on the Formation of Charge-Transfer Tetrathiafulvalene Dimers

Abstract

Three transition metal coordination polymers (CPs) based on the redox-active dimethylthio-tetrathiafulvalene-bicarboxylate (L) and 1,3-bi(4-pyridyl)propane (bpp) ligands, formulated as [MnL(bpp)] (1), [CdL(bpp)] (2), and [CdL(bpp)(HO)(CO)]·n(ClO)·n(HO) (3), are crystallographically characterized. Complexes 1 and 2 are isostructural 2-D polymers, and 3 features an unusual 3-D metal-organic framework (MOF). The 3-D MOF is constructed from tetranuclear cluster nodes built through the μ-O bridge of the TTF ligand, which is first found for TTF coordination polymers. It is found that the channel generated by the 3-D MOF exerts a confinement effect on the formation of TTF dimers. The TTF dimers show strong intradimer interaction with partial electron transfer or charge transfer, and hence, the Cd compound 3 has relatively good photocurrent response property in comparison with that of 2-D Cd compound 2.

The Redox Coupling Effect in a Photocatalytic RuII‐PdII Cage with TTF Guest as Electron Relay Mediator for Visible‐Light Hydrogen‐Evolving Promotion

“…TTF is known as aredox-active and electron donor molecule synthesized artificially forty years ago, [43] which is facile to be oxidized to radical-cation species via one-electron process. [44] Thehydrophobic innerspace makes MOC-16 ready to capture TTF guests in aqueous medium; [42,45] therefore,e lectron transfer might occur when TTF is coalesced and interacted with photoredox MOC-16 host, [46][47][48][49] thus enabling TTF to serve as aregulator to tune photo-electronic activity of MOC-16 ( Figure 1).…”

Electrocatalytic Hydrogenation of N2to NH3by MnO: Experimental and Theoretical Investigations

“…Figure 1h,i presents the X-ray photoelectron spectroscopy (XPS) spectra for MnO in Mn 2p and O 1s regions. [39,40] The pyrolysis process of MnCO 3 was characterized by thermogravimetric analysis (TGA), as shown in Figure S3 (Supporting Information). The BE at 531.7 eV is assigned to the O 1s region with O 2− species.…”

The Redox Coupling Effect in a Photocatalytic RuII‐PdII Cage with TTF Guest as Electron Relay Mediator for Visible‐Light Hydrogen‐Evolving Promotion

“…TTF is known as a redox‐active and electron donor molecule synthesized artificially forty years ago, which is facile to be oxidized to radical‐cation species via one‐electron process . The hydrophobic innerspace makes MOC‐16 ready to capture TTF guests in aqueous medium; therefore, electron transfer might occur when TTF is coalesced and interacted with photoredox MOC‐16 host, thus enabling TTF to serve as a regulator to tune photo‐electronic activity of MOC‐16 (Figure ).…”