The formation of guest-mediated π-donor/acceptor stacks within electroactive metal–organic frameworks activates long-range charge mobilization, boosting the electrical conductivity of the doped materials.

Over the past decade anion-π interaction has emerged as a new paradigm of supramolecular chemistry of anions. Taking advantage of the electronic nature of anion-π interaction, we have expanded its boundaries to charge-transfer (CT) and formal electron transfer (ET) events by adjusting the electron-donating and accepting abilities of anions and π-acids, respectively. To establish that ET, CT, and anion-π interactions could take place between different anions and π-acids as long as their electronic and structural properties are conducive, herein, we introduce 3,4,9,10-perylenediimide (PDI-1) that selectively undergoes thermal ET from strong Lewis basic hydroxide and fluoride anions, but remains electronically and optically silent to poor Lewis basic anions, as ET and CT events are turned OFF. These interactions have been fully characterized by UV/Vis, NMR, and EPR spectroscopies. These results demonstrate the generality of anion-induced ET events in aprotic solvents and further refute a notion that strong Lewis basic hydroxide and fluoride ions can only trigger nucleophilic attack to form covalent bonds instead of acting as sacrificial electron donors to π-acids under appropriate conditions.

A new honeycomb-shaped electroactive metal-organic framework (MOF) has been constructed from an electron deficient naphthalenediimide (NDI) ligand equipped with two terminal salicylic acid groups. π-Intercalation of electron-rich planar tetrathiafulvalene (TTF) guests between the NDI ligands stacked along the walls lowers the electronic band gap of the material by ca. 1 eV. An improved electron delocalization through the guest-mediated π-donor/acceptor stacks is attributed to the diminished band gap of the doped material, which forecasts an improved electrical conductivity.

In this study, the in situ sol–gel method has been deployed to prepare the titanium dioxide/multiwalled carbon nanotubes (TiO 2 /MWCNTs) nanocomposite (NCs) powders with varying content of MWCNTs (0.01–1.0 wt %), to construct the dye-sensitized solar cells (DSSCs). First, binder-free NCs were deposited on a transparent-conducting F:SnO 2 (FTO) glass substrate by a doctor-blade technique and then anchored with Ru(II)-based dyes to either N719 or ruthenium phthalocyanine (RuPc). The structural and optical properties and interconnectivity of the materials within the composite are investigated thoroughly by various spectral techniques (XRD, XPS, Raman, FT-IR, and UV–vis), electron microscopy (HRTEM), and BET analysis. The experimental results suggest that the ratio of MWCNTs and TiO 2 in NCs, morphology, and their interconnectivity influenced their structural, optical, and photovoltaic properties significantly. Finally, the photovoltaic performances of the assembled DSSCs with different content of MWCNTs to TiO 2 films anchored with two different dyes were tested under one sun irradiation (100 mW/cm 2 ). The measured current–voltage ( IV ) curve and incident photon-to-current conversion efficiency (IPCE) spectra of TiO 2 /0.1 wt % MWCNTs (T@0.1 C) for N719 dye show three times more power conversion efficiency (η = 6.21%) which is opposed to an efficiency (η = 2.07%) of T@0.1 C for RuPc dye under the same operating conditions.