Tianyang Chen

All Publications

• High-Energy, High-Power Sodium-Ion Batteries from a Layered Organic Cathode JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Chen, T., Wang, J., Tan, B., Zhang, K. J., Banda, H., Zhang, Y., Kim, D., Dinca, M. 2025

  Abstract

  Sodium-ion batteries (SIBs) attract significant attention due to their potential as an alternative energy storage solution, yet challenges persist due to the limited energy density of existing cathode materials. In principle, redox-active organic materials can tackle this challenge because of their high theoretical energy densities. However, electrode-level energy densities of organic electrodes are compromised due to their poor electron/ion transport and severe dissolution. Here, we report the use of a low-bandgap, conductive, and highly insoluble layered metal-free cathode material for SIBs. It exhibits a high theoretical capacity of 355 mAh g-1 per formula unit, enabled by a four-electron redox process, and achieves an electrode-level energy density of 606 Wh kg-1electrode (90 wt % active material) along with excellent cycling stability. It allows for facile two-dimensional Na+ diffusion, which enables a high intrinsic rate capability. Growth of the active cathode material in the presence of as little as 2 wt % carboxyl-functionalized carbon nanotubes improves charge transport and charge transfer kinetics and further enhances the power performance. Altogether, these allow the construction of SIB cells built from an affordable, sustainable organic small molecule, which provide a cathode energy density of 472 Wh kg-1electrode when charging/discharging in 90 s and a top specific power of 31.6 kW kg-1electrode.

  View details for DOI 10.1021/jacs.4c17713

  View details for Web of Science ID 001416026100001

  View details for PubMedID 39904611

• A Layered Organic Cathode for High-Energy, Fast-Charging, and Long-Lasting Li-Ion Batteries ACS CENTRAL SCIENCE Chen, T., Banda, H., Wang, J., Oppenheim, J. J., Franceschi, A., Dincac, M. 2024

  View details for DOI 10.1021/acscentsci.3c01478

  View details for Web of Science ID 001162222900001

• High-rate, high-capacity electrochemical energy storage in hydrogen-bonded fused aromatics JOULE Chen, T., Banda, H., Yang, L., Li, J., Zhang, Y., Parenti, R., Dinca, M. 2023; 7 (5): 986-1002

  View details for DOI 10.1016/j.joule.2023.03.011

  View details for Web of Science ID 001137001100001

• Dimensionality Modulates Electrical Conductivity in Compositionally Constant One-, Two-, and Three-Dimensional Frameworks JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Chen, T., Dou, J., Yang, L., Sun, C., Oppenheim, J. J., Li, J., Dinca, M. 2022; 144 (12): 5583-5593

  Abstract

  We reveal here the construction of Ni-based metal-organic frameworks (MOFs) and conjugated coordination polymers (CCPs) with different structural dimensionalities, including closely π-stacked 1D chains (Ni-1D), aggregated 2D layers (Ni-2D), and a 3D framework (Ni-3D), based on 2,3,5,6-tetraamino-1,4-hydroquinone (TAHQ) and its various oxidized forms. These materials have the same metal-ligand composition but exhibit distinct electronic properties caused by different dimensionalities and supramolecular interactions between SBUs, ligands, and structural motifs. The electrical conductivity of these materials spans nearly 8 orders of magnitude, approaching 0.3 S/cm.

  View details for DOI 10.1021/jacs.2c00614

  View details for Web of Science ID 000799109400046

  View details for PubMedID 35290048

• High-resolution structure of Zn₃(HOTP)₂ (HOTP = hexaoxidotriphenylene), a three-dimensional conductive MOF CHEMICAL SCIENCE Zhang, K. J., Chen, T., Oppenheim, J. J., Yang, L., Palatinus, L., Mueller, P., Van Voorhis, T., Dinca, M. 2025

  Abstract

  Although two-dimensional (2D) electrically conducting metal-organic frameworks (cMOFs) have become prominent due to their numerous potential applications, their structures are often implied or assumed from rather crude powder X-ray diffraction data. Indeed, exceedingly few examples exist of atomic-level structural details coming from single crystal diffraction experiments. Most widely studied among cMOFs are materials based on triphenylene ligands, in particular M3(HOTP)2 (M = Cu, Zn) and [M3(HOTP)2][M3(HOTP)]2 (M = Mg, Ni, Co; H6HOTP = 2,3,6,7,10,11-hexahydroxytriphenylene), which are invariably described as 2D van der Waals materials with sheets of ligands connected by square planar or octahedral metal ions. Here, we employ electron diffraction to show that, unlike the Mg, Co, Ni, and Cu analogs, Zn3(HOTP)2 crystallizes into a three-dimensional network that is analogous to the structures of the lanthanide-based HOTP MOFs. Moreover, similar to the lanthanide frameworks, Zn3(HOTP)2 exhibits incommensurate modulation, likely originating from a frustration between the preferred π-π stacking distance and the Zn-O bond lengths, or from a Peierls distortion. This work reinforces the importance of employing single crystal diffraction measurements for the characterization of conductive MOFs, especially when trying to correlate electronic properties to structural details.

  View details for DOI 10.1039/d5sc00894h

  View details for Web of Science ID 001505445900001

  View details for PubMedID 40510316

  View details for PubMedCentralID PMC12152966

• Continuous and reversible tuning of inter-layer spacings in two-dimensional conductive metal organic frameworks JOURNAL OF MATERIALS CHEMISTRY A Dontireddy, G. M. R., Suman, S., Merino-Gardea, J. L., Javed, A., Wang, J., Chen, T., Kampouri, S., Banda, H. 2025

  View details for DOI 10.1039/d4ta08063g

  View details for Web of Science ID 001432856800001

• Superior Charge Transport in Ni-Diamine Conductive MOFs. Journal of the American Chemical Society Wang, J., Chen, T., Jeon, M., Oppenheim, J. J., Tan, B., Kim, J., Dinca, M. 2024

  Abstract

  Two-dimensional conductive metal-organic frameworks (2D cMOFs) are an emerging class of crystalline van der Waals layered materials with tunable porosity and high electrical conductivity. They have been used in a variety of applications, such as energy storage and conversion, chemiresistive sensing, and quantum information. Although designing new conductive 2D cMOFs and studying their composition/structure-property relationships have attracted significant attention, there are still very few examples of 2D cMOFs that exhibit room-temperature electrical conductivity above 1 S cm-1, the value exhibited by activated carbon, a well-known porous and conductive material that serves in myriad applications. When such high conductivities are achieved, Ni-diamine linkages are often involved, yet Ni-diamine MOFs remain difficult to access. Here, we report two new 2D cMOFs made through ortho-diamine connections: M3(HITT)2 (M = Ni, Cu; HITT = 2,3,7,8,12,13-hexaiminotetraazanaphthotetraphene). The electrical conductivity of Ni3(HITT)2 reaches 4.5 S cm-1 at 298 K, whereas the conductivity of Cu3(HITT)2 spans from 0.05 (2Cu+Cu2+) to 10-6 (3Cu2+) upon air oxidation, much lower than that of Ni3(HITT)2. Spectroscopic analysis reveals that Ni3(HITT)2 exhibits significantly stronger in-plane pi-d conjugation and higher density of charge carriers compared to Cu3(HITT)2, accounting for the higher electrical conductivity of Ni3(HITT)2. Cu2+/Cu+ mixed valency modulates the energy level and carrier density of Cu3(HITT)2, allowing for a variation of electrical conductivity over 4 orders of magnitude. This work provides a deeper understanding of the influence of metal nodes on electrical conductivity and confirms ortho-diamine linkers as privileged among ligands for 2D cMOFs.

  View details for DOI 10.1021/jacs.4c06935

  View details for PubMedID 39007301

• Arresting dissolution of two-dimensional metal-organic frameworks enables long life in electrochemical devices. Chemical science Dontireddy, G. M., Suman, S. P., Merino-Gardea, J. L., Chen, T., Dou, J. H., Banda, H. 2024; 15 (27): 10416-10424

  Abstract

  Two-dimensional conjugated metal-organic frameworks (2D cMOFs) are emerging as promising materials for electrochemical energy storage (EES). Despite considerable interest, an understanding of their electrochemical stability and the factors contributing to their degradation during cycling is largely lacking. Here we investigate three Cu-based MOFs and report that the dissolution of 2D cMOFs into electrolytes is a prevalent and significant degradation pathway. Several factors, such as the inherent solubility of ligands in electrolyte solvents and the duration of charge-discharge cycling exert a strong influence on the dissolution process. When these factors combine within a MOF, severely limited cycling stability is observed, with dissolution accounting for up to 80% of capacity degradation. Conversely, excellent cycling stability is observed when testing a Cu-MOF with a sparingly soluble ligand within an optimized potential window. Overall, these findings represent essential insights into the electrochemical stability of 2D cMOFs, offering crucial guidelines for their targeted development in EES applications.

  View details for DOI 10.1039/d4sc02699c

  View details for PubMedID 38994412

  View details for PubMedCentralID PMC11234863

• Arresting dissolution of two-dimensional metal-organic frameworks enables long life in electrochemical devices CHEMICAL SCIENCE Dontireddy, G. M. R., Suman, S., Merino-Gardea, J. L., Chen, T., Dou, J., Banda, H. 2024

  View details for DOI 10.1039/d4sc02699c

  View details for Web of Science ID 001241910300001

• Cooperative Interactions with Water Drive Hysteresis in a Hydrophilic Metal-Organic Framework CHEMISTRY OF MATERIALS Oppenheim, J. J., Ho, C., Alezi, D., Andrews, J. L., Chen, T., Dinakar, B., Paesani, F., Dinca, M. 2024

  View details for DOI 10.1021/acs.chemmater.4c00172

  View details for Web of Science ID 001191252600001

• Enhanced Redox Storage and Diverse Intercalation in Layered Metal Organic Frameworks with a Staggered Stacking Mode ACS ENERGY LETTERS Suman, S., Dontireddy, G. M. R., Chen, T., Wang, J., Dou, J., Banda, H. 2024

  View details for DOI 10.1021/acsenergylett.4c00544

  View details for Web of Science ID 001187255100001

• Pyrogallate-Based Metal-Organic Framework with a Two-Dimensional Secondary Building Unit ANGEWANDTE CHEMIE-INTERNATIONAL EDITION Kampouri, S., Zhang, M., Chen, T., Oppenheim, J. J., Brown, A. C., Payne, M. T., Andrews, J. L., Sun, J., Dinca, M. 2022; 61 (49): e202213960

  Abstract

  We report a metal-organic framework (MOF) with a rare two-dimensional (2D) secondary building unit (SBU). The SBU comprises mixed-valent Fe2+ and Fe3+ metal ions bridged by oxygen atoms pertaining to the polytopic ligand 3,3',4,4',5,5'-hexahydroxybiphenyl, which also define the iron-oxide 2D layers. Overall, the anionic framework exhibits rare topology and evidences strong electronic communication between the mixed-valence iron sites. These results highlight the importance of dimensionality control of MOF SBUs for discovering new topologies in reticular chemistry, and especially for improving electronic communication within the MOF skeleton.

  View details for DOI 10.1002/anie.202213960

  View details for Web of Science ID 000879470400001

  View details for PubMedID 36178633

  View details for PubMedCentralID PMC10100382

• Room-Temperature Quantitative Quantum Sensing of Lithium Ions with a Radical-Embedded Metal-Organic Framework JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Sun, L., Yang, L., Dou, J., Li, J., Skorupskii, G., Mardini, M., Tan, K., Chen, T., Sun, C., Oppenheim, J. J., Griffin, R. G., Dinca, M., Rajh, T. 2022; 144 (41): 19008-19016

  Abstract

  Recent advancements in quantum sensing have sparked transformative detection technologies with high sensitivity, precision, and spatial resolution. Owing to their atomic-level tunability, molecular qubits and ensembles thereof are promising candidates for sensing chemical analytes. Here, we show quantum sensing of lithium ions in solution at room temperature with an ensemble of organic radicals integrated in a microporous metal-organic framework (MOF). The organic radicals exhibit electron spin coherence and microwave addressability at room temperature, thus behaving as qubits. The high surface area of the MOF promotes accessibility of the guest analytes to the organic qubits, enabling unambiguous identification of lithium ions and quantitative measurement of their concentration through relaxometric and hyperfine spectroscopic methods based on electron paramagnetic resonance (EPR) spectroscopy. The sensing principle presented in this work is applicable to other metal ions with nonzero nuclear spin.

  View details for DOI 10.1021/jacs.2c07692

  View details for Web of Science ID 000875645600001

  View details for PubMedID 36201712

• Porous lanthanide metal-organic frameworks with metallic conductivity PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA Skorupskii, G., Le, K. N., Cordova, D., Yang, L., Chen, T., Hendon, C. H., Arguilla, M. Q., Dinca, M. 2022; 119 (34): e2205127119

  Abstract

  Metallic charge transport and porosity appear almost mutually exclusive. Whereas metals demand large numbers of free carriers and must have minimal impurities and lattice vibrations to avoid charge scattering, the voids in porous materials limit the carrier concentration, provide ample space for impurities, and create more charge-scattering vibrations due to the size and flexibility of the lattice. No microporous material has been conclusively shown to behave as a metal. Here, we demonstrate that single crystals of the porous metal-organic framework Ln1.5(2,3,6,7,10,11-hexaoxytriphenylene) (Ln = La, Nd) are metallic. The materials display the highest room-temperature conductivities of all porous materials, reaching values above 1,000 S/cm. Single crystals of the compounds additionally show clear temperature-deactivated charge transport, a hallmark of a metallic material. Lastly, a structural transition consistent with charge density wave ordering, present only in metals and rare in any materials, provides additional conclusive proof of the metallic nature of the materials. Our results provide an example of a metal with porosity intrinsic to its structure. We anticipate that the combination of porosity and chemical tunability that these materials possess will provide a unique handle toward controlling the unconventional states that lie within them, such as charge density waves that we observed, or perhaps superconductivity.

  View details for DOI 10.1073/pnas.2205127119

  View details for Web of Science ID 001025718500005

  View details for PubMedID 35969747

  View details for PubMedCentralID PMC9407220

• Thousand-fold increase in O2 electroreduction rates with conductive MOFs. ACS central science Mariano, R. G., Wahab, O. J., Rabinowitz, J. A., Oppenheim, J., Chen, T., Unwin, P. R., Dincǎ, M. 2022; 8 (7): 975-982

  Abstract

  Molecular materials must deliver high current densities to be competitive with traditional heterogeneous catalysts. Despite their high density of active sites, it has been unclear why the reported O2 reduction reaction (ORR) activity of molecularly defined conductive metal-organic frameworks (MOFs) have been very low: ca. -1 mA cm-2. Here, we use a combination of gas diffusion electrolyses and nanoelectrochemical measurements to lift multiscale O2 transport limitations and show that the intrinsic electrocatalytic ORR activity of a model 2D conductive MOF, Ni3(HITP)2, has been underestimated by at least 3 orders of magnitude. When it is supported on a gas diffusion electrode (GDE), Ni3(HITP)2 can deliver ORR activities >-150 mA cm-2 and gravimetric H2O2 electrosynthesis rates exceeding or on par with those of prior heterogeneous electrocatalysts. Enforcing the fastest accessible mass transport rates using scanning electrochemical cell microscopy revealed that Ni3(HITP)2 is capable of ORR current densities exceeding -1200 mA cm-2 and at least another 130-fold higher ORR mass activity than has been observed in GDEs. Our results directly implicate precise control over multiscale mass transport to achieve high-current-density electrocatalysis in molecular materials.

  View details for DOI 10.1021/acscentsci.2c00509

  View details for PubMedID 35912352

  View details for PubMedCentralID PMC9336150

• Thousand-fold increase in O-2 electroreduction rates with conductive MOFs ACS CENTRAL SCIENCE Mariano, R. G., Wahab, O. J., Rabinowitz, J. A., Oppenheim, J., Chen, T., Unwin, P. R., Dinca, M. 2022

  View details for DOI 10.1021/acscentsci.2c00509

  View details for Web of Science ID 000826305200001

• Atomically precise single-crystal structures of electrically conducting 2D metal-organic frameworks NATURE MATERIALS Dou, J., Arguilla, M. Q., Luo, Y., Li, J., Zhang, W., Sun, L., Mancuso, J. L., Yang, L., Chen, T., Parent, L. R., Skorupskii, G., Libretto, N. J., Sun, C., Yang, M., Dip, P., Brignole, E. J., Miller, J. T., Kong, J., Hendon, C. H., Sun, J., Dinca, M. 2021; 20 (2): 222-+

  Abstract

  Electrically conducting 2D metal-organic frameworks (MOFs) have attracted considerable interest, as their hexagonal 2D lattices mimic graphite and other 2D van der Waals stacked materials. However, understanding their intrinsic properties remains a challenge because their crystals are too small or of too poor quality for crystal structure determination. Here, we report atomically precise structures of a family of 2D π-conjugated MOFs derived from large single crystals of sizes up to 200 μm, allowing atomic-resolution analysis by a battery of high-resolution diffraction techniques. A designed ligand core rebalances the in-plane and out-of-plane interactions that define anisotropic crystal growth. We report two crystal structure types exhibiting analogous 2D honeycomb-like sheets but distinct packing modes and pore contents. Single-crystal electrical transport measurements distinctively demonstrate anisotropic transport normal and parallel to the π-conjugated sheets, revealing a clear correlation between absolute conductivity and the nature of the metal cation and 2D sheet packing motif.

  View details for DOI 10.1038/s41563-020-00847-7

  View details for Web of Science ID 000592020100002

  View details for PubMedID 33230325

• 2-Butene Tetraanion Bridged Dinuclear Samarium(III) Complexes via Sm(II)-Mediated Reduction of Electron-Rich Olefins JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Zheng, Y., Cao, C., Ma, W., Chen, T., Wu, B., Yu, C., Huang, Z., Yin, J., Hu, H., Li, J., Zhang, W., Xi, Z. 2020; 142 (24): 10705-10714

  Abstract

  While reduction reactions are ubiquitous in chemistry, it is very challenging to further reduce electron-rich compounds, especially the anionic ones. In this work, the reduction of 1,3-butadienyl dianion, the anionic conjugated olefin, has been realized by divalent rare-earth metal compounds (SmI2), resulting in the formation of novel 2-butene tetraanion bridged disamarium(III) complexes. Density functional theory (DFT) analyses reveal two features: (i) the single electron transfer (SET) from 4f atomic orbitals (AOs) of each Sm center to the antibonding π*-orbitals of 1,3-butadienyl dianion is feasible and the new HOMO formed by the bonding interaction between Sm 5d orbitals (AOs) and the π*-orbitals of 1,3-butadienyl dianion can accept favorably 2e- from 4f AOs of Sm(II); (ii) the 2-butene tetraanionic ligand serves as a unique 10e- donating system, in which 4e- act as two σ-donation bonding interactions while the rest 6e- as three π-donation bonding interactions. The disamarium(III) complexes represent a unique class of the bridged bis-alkylidene rare-earth organometallic complexes. The ligand-based reductive reactivity of 2-butene tetraanion bridged disamarium(III) complexes demonstrates that 2-butene tetraanionic ligand serves as a 3e- reductant toward cyclooctatetraene (COT) to provide doubly COT-supported disamarabutadiene complexes. The reaction of the disamarium(III) complexes with Cp*Li produces the doubly Cp*-coordinated Sm(III) complexes via salt metathesis. In addition, the reaction with Mo(CO)6 affords the oxycyclopentadienyl dinuclear complex via CO insertion.

  View details for DOI 10.1021/jacs.0c01690

  View details for Web of Science ID 000542929600015

  View details for PubMedID 32408744

• Dilithio Spiro Zincacyclopentadienes and Dizinca[10]cycles: Synthesis and Structural Characterization ORGANOMETALLICS Zhang, Y., Liu, L., Chen, T., Huang, Z., Zhang, W., Xi, Z. 2019; 38 (9): 2174-2178

  View details for DOI 10.1021/acs.organomet.9b00154

  View details for Web of Science ID 000468120200035

• Formation and ligand-based reductive chemistry of bridged bis-alkylidene scandium(III) complexes CHEMICAL SCIENCE Ma, W., Yu, C., Chi, Y., Chen, T., Wang, L., Yin, J., Wei, B., Xu, L., Zhang, W., Xi, Z. 2017; 8 (10): 6852-6856

  Abstract

  The chemistry of rare-earth carbene and alkylidene complexes including their synthesis, structure and reaction is a challenging issue because of their high reactivity (or instability) and the lack of synthetic methods. In this work, we report the first synthesis of the bridged bis-alkylidene complexes which feature a 2-butene-1,1,4,4-tetraanion and four Sc-C(sp3) bonds by the reaction of 1,4-dilithio-1,3-butadienes with ScCl3. This reaction proceeds via two key intermediates: an isolable scandacyclopentadiene and a proposed scandacyclopropene. The scandacyclopentadiene undergoes β,β'-C-C bond cleavage to generate the scandacyclopropene, which then dimerizes to afford the bridged bis-alkylidene complex via a cooperative double metathesis reaction. Reaction chemistry study of the bridged bis-alkylidene complex reveals their ligand-based reduction reactivity towards different oxidants such as hexachloroethane, disulfide and cyclooctatetraene.

  View details for DOI 10.1039/c7sc02018j

  View details for Web of Science ID 000411730500014

  View details for PubMedID 29147510

  View details for PubMedCentralID PMC5632790