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1. Effects of intervalence charge transfer interaction between π-stacked mixed valent tetrathiafulvalene ligands on the electrical conductivity of 3D metal–organic frameworks

   https://doi.org/10.1039/d1sc04338b  

   Zhang, Shiyu ; Panda, Dillip K. ; Yadav, Ashok ; Zhou, Wei ; Saha, Sourav ( October 2021 , Chemical Science)

   Achieving a molecular-level understanding of how the structures and compositions of metal–organic frameworks (MOFs) influence their charge carrier concentration and charge transport mechanism—the two key parameters of electrical conductivity—is essential for the successful development of electrically conducting MOFs, which have recently emerged as one of the most coveted functional materials due to their diverse potential applications in advanced electronics and energy technologies. Herein, we have constructed four new alkali metal (Na, K, Rb, and Cs) frameworks based on an electron-rich tetrathiafulvalene tetracarboxylate (TTFTC) ligand, which formed continuous π-stacks, albeit with different π–π-stacking and S⋯S distances ( d π–π and d S⋯S ). These MOFs also contained different amounts of aerobically oxidized TTFTC˙ + radical cations that were quantified by electron spin resonance (ESR) spectroscopy. Density functional theory calculations and diffuse reflectance spectroscopy demonstrated that depending on the π–π-interaction and TTFTC˙ + population, these MOFs enjoyed varying degrees of TTFTC/TTFTC˙ + intervalence charge transfer (IVCT) interactions, which commensurately affected their electronic and optical band gaps and electrical conductivity. Having the shortest d π–π (3.39 Å) and the largest initial TTFTC˙ + population (∼23%), the oxidized Na-MOF 1-ox displayed the narrowest band gap (1.33 eV) and the highest room temperature electrical conductivitymore »(3.6 × 10 −5 S cm −1 ), whereas owing to its longest d π–π (3.68 Å) and a negligible TTFTC˙ + population, neutral Cs-MOF 4 exhibited the widest band gap (2.15 eV) and the lowest electrical conductivity (1.8 × 10 −7 S cm −1 ). The freshly prepared but not optimally oxidized K-MOF 2 and Rb-MOF 3 initially displayed intermediate band gaps and conductivity, however, upon prolonged aerobic oxidation, which raised the TTFTC˙ + population to saturation levels (∼25 and 10%, respectively), the resulting 2-ox and 3-ox displayed much narrower band gaps (∼1.35 eV) and higher electrical conductivity (6.6 × 10 −5 and 4.7 × 10 −5 S cm −1 , respectively). The computational studies indicated that charge movement in these MOFs occurred predominantly through the π-stacked ligands, while the experimental results displayed the combined effects of π–π-interactions, TTFTC˙ + population, and TTFTC/TTFTC˙ + IVCT interaction on their electronic and optical properties, demonstrating that IVCT interactions between the mixed-valent ligands could be exploited as an effective design strategy to develop electrically conducting MOFs.« less
2. A New Electrically Conducting Metal–Organic Framework Featuring U-Shaped cis-Dipyridyl Tetrathiafulvalene Ligands

   https://doi.org/10.3389/fchem.2021.726544  

   Gordillo, Monica A. ; Benavides, Paola A. ; Spalding, Kaybriana ; Saha, Sourav ( October 2021 , Frontiers in Chemistry)

   A new electrically conducting 3D metal-organic framework (MOF) with a unique architecture was synthesized using 1,2,4,5-tetrakis-(4-carboxyphenyl)benzene (TCPB) a redox-active cis -dipyridyl-tetrathiafulvalene ( Z -DPTTF) ligand. While TCPB formed Zn 2 (COO) 4 secondary building units (SBUs), instead of connecting the Zn 2 -paddlewheel SBUs located in different planes and forming a traditional pillared paddlewheel MOF, the U-shaped Z -DPTTF ligands bridged the neighboring SBUs formed by the same TCPB ligand like a sine-curve along the b axis that created a new sine -MOF architecture. The pristine sine -MOF displayed an intrinsic electrical conductivity of 1 × 10 −8  S/m, which surged to 5 × 10 −7  S/m after I 2 doping due to partial oxidation of electron rich Z -DPTTF ligands that raised the charge-carrier concentration inside the framework. However, the conductivities of the pristine and I 2 -treated sine -MOFs were modest possibly because of large spatial distances between the ligands that prevented π-donor/acceptor charge-transfer interactions needed for effective through-space charge movement in 3D MOFs that lack through coordination-bond charge transport pathways.
3. 2D Copper Tetrahydroxyquinone Conductive Metal–Organic Framework for Selective CO ₂ Electrocatalysis at Low Overpotentials

   https://doi.org/10.1002/adma.202004393  

   Majidi, Leily ; Ahmadiparidari, Alireza ; Shan, Nannan ; Misal, Saurabh N. ; Kumar, Khagesh ; Huang, Zhehao ; Rastegar, Sina ; Hemmat, Zahra ; Zou, Xiaodong ; Zapol, Peter ; et al ( February 2021 , Advanced Materials)

   Metal–organic frameworks (MOFs) are promising materials for electrocatalysis; however, lack of electrical conductivity in the majority of existing MOFs limits their effective utilization in the field. Herein, an excellent catalytic activity of a 2D copper (Cu)‐based conductive MOF, copper tetrahydroxyquinone (CuTHQ), is reported for aqueous CO₂reduction reaction (CO₂RR) at low overpotentials. It is revealed that CuTHQ nanoflakes (NFs) with an average lateral size of 140 nm exhibit a negligible overpotential of 16 mV for the activation of this reaction, a high current density of ≈173 mA cm⁻²at −0.45 V versus RHE, an average Faradaic efficiency (F.E.) of ≈91% toward CO production, and a remarkable turnover frequency as high as ≈20.82 s⁻¹. In the low overpotential range, the obtained CO formation current density is more than 35 and 25 times higher compared to state‐of‐the‐art MOF and MOF‐derived catalysts, respectively. The operando Cu K‐edge X‐ray absorption near edge spectroscopy and density functional theory calculations reveal the existence of reduced Cu (Cu⁺) during CO₂RR which reversibly returns to Cu²⁺after the reaction. The outstanding CO₂catalytic functionality of conductive MOFs (c‐MOFs) can open a way toward high‐energy‐density electrochemical systems.
4. Design and synthesis of two-dimensional covalent organic frameworks with four-arm cores: prediction of remarkable ambipolar charge-transport properties

   https://doi.org/10.1039/C9MH00035F  

   Thomas, Simil ; Li, Hong ; Dasari, Raghunath R. ; Evans, Austin M. ; Castano, Ioannina ; Allen, Taylor G. ; Reid, Obadiah G. ; Rumbles, Garry ; Dichtel, William R. ; Gianneschi, Nathan C. ; et al ( January 2019 , Materials Horizons)

   We have considered three two-dimensional (2D) π-conjugated polymer network ( i.e. , covalent organic frameworks, COFs) materials based on pyrene, porphyrin, and zinc-porphyrin cores connected via diacetylenic linkers. Their electronic structures, investigated at the density functional theory global-hybrid level, are indicative of valence and conduction bands that have large widths, ranging between 1 and 2 eV. Using a molecular approach to derive the electronic couplings between adjacent core units and the electron-vibration couplings, the three π-conjugated 2D COFs are predicted to have ambipolar charge-transport characteristics with electron and hole mobilities in the range of 65–95 cm 2 V −1 s −1 . Such predicted values rank these 2D COFs among the highest-mobility organic semiconductors. In addition, we have synthesized the zinc-porphyrin based 2D COF and carried out structural characterization via powder X-ray diffraction, high-resolution transmission electron microscopy, and surface area analysis, which demonstrates the feasibility of these electroactive networks. Steady-state and flash-photolysis time-resolved microwave conductivity measurements on the zinc-porphyrin COF point to appreciable, broadband photoconductivity while transmission spectral measurements are indicative of extended π-conjugation.
5. Correction to “From n- to p-Type Material: Effect of Metal Ion on Charge Transport in Metal–Organic Materials”

   https://doi.org/10.1021/acsami.2c05799  

   Yoon, Sungwon ; Talin, A. Alec ; Stavila, Vitalie ; Mroz, Austin M. ; Bennett, Thomas D. ; He, Yuping ; Keen, David A. ; Hendon, Christopher H. ; Allendorf, Mark D. ; So, Monica C. ( April 2022 , ACS Applied Materials & Interfaces)

   An intriguing new class of two-dimensional (2D) materials based on metal–organic frameworks (MOFs) has recently been developed that displays electrical conductivity, a rarity among these nanoporous materials. The emergence of conducting MOFs raises questions about their fundamental electronic properties, but few studies exist in this regard. Here, we present an integrated theory and experimental investigation to probe the effects of metal substitution on the charge transport properties of M-HITP, where M = Ni or Pt and HITP = 2,3,6,7,10,11-hexaiminotriphenylene. The results show that the identity of the M-HITP majority charge carrier can be changed without intentional introduction of electronically active dopants. We observe that the selection of the metal ion substantially affects charge transport. Using the known structure, Ni-HITP, we synthesized a new amorphous material, a-Pt-HITP, which although amorphous is nevertheless found to be porous upon desolvation. Importantly, this new material exhibits p-type charge transport behavior, unlike Ni-HITP, which displays n-type charge transport. These results demonstrate that both p- and n-type materials can be achieved within the same MOF topology through appropriate choice of the metal ion.