Metal–Carbodithioate-Based 3D Semiconducting Metal–Organic Framework: Porous Optoelectronic Material for Energy Conversion

Li, Xinlin; Anderson, Ryther; Fry, H. Christopher; Pratik, Saied Md.; Xu, Wenqian; Goswami, Subhadip; Allen, Taylor G.; Yu, Jierui; Rajasree, Sreehari Surendran; Cramer, Christopher J.; Rumbles, Garry; Gómez-Gualdrón, Diego A.; Deria, Pravas

doi:10.1021/acsami.3c04200

Metal–Carbodithioate-Based 3D Semiconducting Metal–Organic Framework: Porous Optoelectronic Material for Energy Conversion

Journal Article · Wed May 31 00:00:00 EDT 2023 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.3c04200· OSTI ID:2404851

^[1]; Anderson, Ryther ^[2]; ^[3]; ^[4]; Xu, Wenqian ^[5]; ^[6]; Allen, Taylor G. ^[7]; Yu, Jierui ^[1]; Rajasree, Sreehari Surendran ^[1]; ^[4]; ^[8]; Gómez-Gualdrón, Diego A. ^[2]; ^[1]

Southern Illinois Univ., Carbondale, IL (United States)
Colorado School of Mines, Golden, CO (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States). Center for Nanoscale Materials (CNM)
Univ. of Minnesota, Minneapolis, MN (United States). Minnesota Supercomputing Inst.
Argonne National Laboratory (ANL), Argonne, IL (United States)
Northwestern Univ., Evanston, IL (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States); Univ. of Colorado, Boulder, CO (United States). Renewable and Sustainable Energy Institute (RSEI)

Solar energy conversion requires the working compositions to generate photoinduced charges with high potential and the ability to deliver charges to the catalytic sites and/or external electrode. These two properties are typically at odds with each other and call for new molecular materials with sufficient conjugation to improve charge conductivity but not as much conjugation as to overly compromise the optical band gap. In this work, we developed a semiconducting metal-organic framework (MOF) prepared explicitly through metal-carbodithioate"(-CS₂)_nM" linkage chemistry, entailing augmented metal-linker electronic communication. The stronger ligand field and higher covalent character of metal-carbodithioate linkages-when combined with spirofluorene-derived organic struts and nickel-(II) ion-based nodes-provided a stable, semiconducting 3D-porous MOF, Spiro-CS₂Ni. This MOF lacks long-range ordering and is defined by a flexible structure with non-aggregated building units, as suggested by reverse Monte Carlo simulations of the pair distribution function obtained from total scattering experiments. The solvent-removed "closed pore"material recorded a Brunauer-Emmett-Teller area of similar to 400m²/g, where the "open pore" form possesses90 wt % solvent-accessible porosity. Electrochemical measurements suggest that Spiro-CS₂Ni possesses a band gap of 1.57 eV(sigma = 10^-7 S/cm at -1.3 V bias potential),which can be further improved by manipulating the d-electron configuration through an axial coordination (ligand/substrate), the latter of which indicates usefulness as an electrocatalyst and/or a photoelectrocatalyst(upon substrate binding). Transient-absorption spectroscopy reveals a long-lived photo-generated charge-transfer state (τ_CR = 6.5 mu s) capable of chemical transformation under a biased voltage. Spiro-CS₂Ni can endure a compelling range of pH(1-12 for weeks) and hours of electrochemical and photoelectrochemical conditions in the presence of water and organic acids. We believe this work provides crucial design principles for low-density, porous,light-energy-conversion materials.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; AC36-08GO28308

OSTI ID:: 2404851

Alternate ID(s):: OSTI ID: 1986124

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 23 Vol. 15; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (56)

Semiconductor Metal-Organic Frameworks: Future Low-Bandgap Materials Usman, Muhammad; Mendiratta, Shruti; Lu, Kuang-Lieh Advanced Materials, Vol. 29, Issue 6 https://doi.org/10.1002/adma.201605071	journal	November 2016
A Hybrid Solid with Giant Pores Prepared by a Combination of Targeted Chemistry, Simulation, and Powder Diffraction Férey, Gérard; Serre, Christian; Mellot-Draznieks, Caroline Angewandte Chemie International Edition, Vol. 43, Issue 46 https://doi.org/10.1002/anie.200460592	journal	August 2004
Zirconium-Metalloporphyrin PCN-222: Mesoporous Metal-Organic Frameworks with Ultrahigh Stability as Biomimetic Catalysts Feng, Dawei; Gu, Zhi-Yuan; Li, Jian-Rong Angewandte Chemie International Edition, Vol. 51, Issue 41 https://doi.org/10.1002/anie.201204475	journal	August 2012
Electrically Conductive Porous Metal-Organic Frameworks Sun, Lei; Campbell, Michael G.; Dincă, Mircea Angewandte Chemie International Edition, Vol. 55, Issue 11 https://doi.org/10.1002/anie.201506219	journal	January 2016
Fulleretic Well-Defined Scaffolds: Donor-Fullerene Alignment Through Metal Coordination and Its Effect on Photophysics Williams, Derek E.; Dolgopolova, Ekaterina A.; Godfrey, Danielle C. Angewandte Chemie International Edition, Vol. 55, Issue 31 https://doi.org/10.1002/anie.201603584	journal	June 2016
Tuning Single‐Molecule Conductance in Metalloporphyrin‐Based Wires via Supramolecular Interactions Aragonès, Albert C.; Martín‐Rodríguez, Alejandro; Aravena, Daniel Angewandte Chemie International Edition, Vol. 59, Issue 43 https://doi.org/10.1002/anie.202007237	journal	August 2020
Optical and Transport Properties of Metals Grosso, Giuseppe; Parravicini, Giuseppe Pastori Solid State Physics https://doi.org/10.1016/B978-0-12-385030-0.00011-6	book	January 2014
Electrically Conductive Metal–Organic Frameworks Xie, Lilia S.; Skorupskii, Grigorii; Dincă, Mircea Chemical Reviews https://doi.org/10.1021/acs.chemrev.9b00766	journal	April 2020
Synthesis of a Zr-Based Metal–Organic Framework with Spirobifluorenetetrabenzoic Acid for the Effective Removal of Nerve Agent Simulants Park, Hea Jung; Jang, Jin Kyu; Kim, Seo-Yul Inorganic Chemistry, Vol. 56, Issue 20 https://doi.org/10.1021/acs.inorgchem.7b02022	journal	October 2017
One-Dimensional Chains of Paddlewheel-Type Dichromium(II,II) Tetraacetate Complexes: Study of Electronic Structure Influenced by σ- and π-Donation of Axial Linkers Huang, Po-Jung; Natori, Yoshiki; Kitagawa, Yasutaka Inorganic Chemistry, Vol. 57, Issue 9 https://doi.org/10.1021/acs.inorgchem.8b00352	journal	April 2018
Controlling Charge-Transport in Metal–Organic Frameworks: Contribution of Topological and Spin-State Variation on the Iron–Porphyrin Centered Redox Hopping Rate Maindan, Karan; Li, Xinlin; Yu, Jierui The Journal of Physical Chemistry B, Vol. 123, Issue 41 https://doi.org/10.1021/acs.jpcb.9b07506	journal	September 2019
Unraveling the Semiconducting/Metallic Discrepancy in Ni ₃ (HITP) ₂ Foster, Michael E.; Sohlberg, Karl; Allendorf, Mark D. The Journal of Physical Chemistry Letters, Vol. 9, Issue 3 https://doi.org/10.1021/acs.jpclett.7b03140	journal	January 2018
Charge Separation Mechanisms in Ordered Films of Self-Assembled Donor–Acceptor Dyad Ribbons Logsdon, Jenna L.; Hartnett, Patrick E.; Nelson, Jordan N. ACS Applied Materials & Interfaces, Vol. 9, Issue 39 https://doi.org/10.1021/acsami.7b02585	journal	April 2017
Light-Harvesting “Antenna” Behavior in NU-1000 Goswami, Subhadip; Yu, Jierui; Patwardhan, Sameer ACS Energy Letters, Vol. 6, Issue 3 https://doi.org/10.1021/acsenergylett.0c02514	journal	February 2021
Light-Harvesting in Porous Crystalline Compositions: Where We Stand toward Robust Metal–Organic Frameworks Yu, Jierui; Li, Xinlin; Deria, Pravas ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 2 https://doi.org/10.1021/acssuschemeng.8b05673	journal	December 2018
Chlorophyll J-Aggregates: From Bioinspired Dye Stacks to Nanotubes, Liquid Crystals, and Biosupramolecular Electronics Sengupta, Sanchita; Würthner, Frank Accounts of Chemical Research, Vol. 46, Issue 11 https://doi.org/10.1021/ar400017u	journal	July 2013
Amorphous Metal–Organic Frameworks Bennett, Thomas D.; Cheetham, Anthony K. Accounts of Chemical Research, Vol. 47, Issue 5 https://doi.org/10.1021/ar5000314	journal	April 2014
Self-Assembly Strategies for Integrating Light Harvesting and Charge Separation in Artificial Photosynthetic Systems Wasielewski, Michael R. Accounts of Chemical Research, Vol. 42, Issue 12 https://doi.org/10.1021/ar9001735	journal	December 2009
Conductivity, Doping, and Redox Chemistry of a Microporous Dithiolene-Based Metal−Organic Framework Kobayashi, Yoji; Jacobs, Benjamin; Allendorf, Mark D. Chemistry of Materials, Vol. 22, Issue 14 https://doi.org/10.1021/cm101238m	journal	July 2010
Dynamic aspects of semiconductor photoelectrochemistry Peter, Lawrence M. Chemical Reviews, Vol. 90, Issue 5 https://doi.org/10.1021/cr00103a005	journal	July 1990
Synthesis of Metal-Organic Frameworks (MOFs): Routes to Various MOF Topologies, Morphologies, and Composites Stock, Norbert; Biswas, Shyam Chemical Reviews, Vol. 112, Issue 2 https://doi.org/10.1021/cr200304e	journal	September 2011
Synthesis, Structure, and Metalation of Two New Highly Porous Zirconium Metal–Organic Frameworks Morris, William; Volosskiy, Boris; Demir, Selcuk Inorganic Chemistry, Vol. 51, Issue 12, p. 6443-6445 https://doi.org/10.1021/ic300825s	journal	June 2012
Complexes of dithiocarboxylic acids Furlani, C.; Luciani, M. L. Inorganic Chemistry, Vol. 7, Issue 8 https://doi.org/10.1021/ic50066a021	journal	August 1968
Self-Assembling Light-Harvesting Systems from Synthetically Modified Tobacco Mosaic Virus Coat Proteins Miller, Rebekah A.; Presley, Andrew D.; Francis, Matthew B. Journal of the American Chemical Society, Vol. 129, Issue 11 https://doi.org/10.1021/ja063887t	journal	March 2007
Vapor-Phase Metalation by Atomic Layer Deposition in a Metal–Organic Framework Mondloch, Joseph E.; Bury, Wojciech; Fairen-Jimenez, David Journal of the American Chemical Society, Vol. 135, Issue 28, p. 10294-10297 https://doi.org/10.1021/ja4050828	journal	May 2013
Stepwise Assembly of Pd ₆ (RuL ₃ ) ₈ Nanoscale Rhombododecahedral Metal–Organic Cages via Metalloligand Strategy for Guest Trapping and Protection Li, Kang; Zhang, Lu-Yin; Yan, Cheng Journal of the American Chemical Society, Vol. 136, Issue 12 https://doi.org/10.1021/ja410044r	journal	March 2014
Solvothermal Preparation of an Electrocatalytic Metalloporphyrin MOF Thin Film and its Redox Hopping Charge-Transfer Mechanism Ahrenholtz, Spencer R.; Epley, Charity C.; Morris, Amanda J. Journal of the American Chemical Society, Vol. 136, Issue 6 https://doi.org/10.1021/ja410684q	journal	January 2014
Two-Dimensional Metal–Organic Surfaces for Efficient Hydrogen Evolution from Water Clough, Andrew J.; Yoo, Joseph W.; Mecklenburg, Matthew H. Journal of the American Chemical Society, Vol. 137, Issue 1 https://doi.org/10.1021/ja5116937	journal	December 2014
A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability Cavka, Jasmina Hafizovic; Jakobsen, Søren; Olsbye, Unni Journal of the American Chemical Society, Vol. 130, Issue 42, p. 13850-13851 https://doi.org/10.1021/ja8057953	journal	October 2008
Supercritical Processing as a Route to High Internal Surface Areas and Permanent Microporosity in Metal−Organic Framework Materials Nelson, Andrew P.; Farha, Omar K.; Mulfort, Karen L. Journal of the American Chemical Society, Vol. 131, Issue 2, p. 458-460 https://doi.org/10.1021/ja808853q	journal	January 2009
Optimizing Single-Molecule Conductivity of Conjugated Organic Oligomers with Carbodithioate Linkers Xing, Yangjun; Park, Tae-Hong; Venkatramani, Ravindra Journal of the American Chemical Society, Vol. 132, Issue 23 https://doi.org/10.1021/ja909559m	journal	April 2010
Improving Energy Transfer within Metal–Organic Frameworks by Aligning Linker Transition Dipoles along the Framework Axis Yu, Jierui; Anderson, Ryther; Li, Xinlin Journal of the American Chemical Society, Vol. 142, Issue 25 https://doi.org/10.1021/jacs.0c03949	journal	May 2020
Photoinduced Charge Transfer with a Small Driving Force Facilitated by Exciplex-like Complex Formation in Metal–Organic Frameworks Li, Xinlin; Yu, Jierui; Lu, Zhiyong Journal of the American Chemical Society, Vol. 143, Issue 37 https://doi.org/10.1021/jacs.1c06629	journal	September 2021
Semiconductor Porous Hydrogen-Bonded Organic Frameworks Based on Tetrathiafulvalene Derivatives Vicent-Morales, María; Esteve-Rochina, María; Calbo, Joaquín Journal of the American Chemical Society, Vol. 144, Issue 20 https://doi.org/10.1021/jacs.2c01957	journal	May 2022
Ultraporous, Water Stable, and Breathing Zirconium-Based Metal–Organic Frameworks with ftw Topology Deria, Pravas; Gómez-Gualdrón, Diego A.; Bury, Wojciech Journal of the American Chemical Society, Vol. 137, Issue 40 https://doi.org/10.1021/jacs.5b08860	journal	September 2015
Porous Field-Effect Transistors Based on a Semiconductive Metal–Organic Framework Wu, Guodong; Huang, Jiahong; Zang, Ying Journal of the American Chemical Society, Vol. 139, Issue 4 https://doi.org/10.1021/jacs.6b08511	journal	November 2016
Metallic Conductivity in a Two-Dimensional Cobalt Dithiolene Metal–Organic Framework Clough, Andrew J.; Skelton, Jonathan M.; Downes, Courtney A. Journal of the American Chemical Society, Vol. 139, Issue 31 https://doi.org/10.1021/jacs.7b05742	journal	July 2017
Signature of Metallic Behavior in the Metal–Organic Frameworks M ₃ (hexaiminobenzene) ₂ (M = Ni, Cu) Dou, Jin-Hu; Sun, Lei; Ge, Yicong Journal of the American Chemical Society, Vol. 139, Issue 39 https://doi.org/10.1021/jacs.7b07234	journal	September 2017
Charge-Transfer within Zr-Based Metal–Organic Framework: The Role of Polar Node Van Wyk, Andrea; Smith, Tanner; Park, Jaehong Journal of the American Chemical Society, Vol. 140, Issue 8 https://doi.org/10.1021/jacs.7b13211	journal	February 2018
Active-Site Modulation in an Fe-Porphyrin-Based Metal–Organic Framework through Ligand Axial Coordination: Accelerating Electrocatalysis and Charge-Transport Kinetics Liberman, Itamar; Shimoni, Ran; Ifraemov, Raya Journal of the American Chemical Society, Vol. 142, Issue 4 https://doi.org/10.1021/jacs.9b11355	journal	January 2020
Energy and Photoinduced Electron Transfer in Porphyrin−Fullerene Dyads Kuciauskas, Darius; Lin, Su; Seely, Gilbert R. The Journal of Physical Chemistry, Vol. 100, Issue 39 https://doi.org/10.1021/jp9612745	journal	January 1996
Highly Conductive Single-Molecule Wires with Controlled Orientation by Coordination of Metalloporphyrins Aragonès, Albert C.; Darwish, Nadim; Saletra, Wojciech J. Nano Letters, Vol. 14, Issue 8 https://doi.org/10.1021/nl501884g	journal	July 2014
Revealing the blueprint of photosynthesis Barber, J.; Andersson, B. Nature, Vol. 370, Issue 6484 https://doi.org/10.1038/370031a0	journal	July 1994
A semiconducting layered metal-organic framework magnet Yang, Chongqing; Dong, Renhao; Wang, Mao Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-11267-w	journal	July 2019
Intrinsic glassy-metallic transport in an amorphous coordination polymer Xie, Jiaze; Ewing, Simon; Boyn, Jan-Niklas Nature, Vol. 611, Issue 7936 https://doi.org/10.1038/s41586-022-05261-4	journal	October 2022
Electrical conductive coordination polymers Givaja, Gonzalo; Amo-Ochoa, Pilar; Gómez-García, Carlos J. Chem. Soc. Rev., Vol. 41, Issue 1 https://doi.org/10.1039/c1cs15092h	journal	January 2012
Powering the future of molecular artificial photosynthesis with light-harvesting metallosupramolecular dye assemblies Frischmann, Peter D.; Mahata, Kingsuk; Würthner, Frank Chem. Soc. Rev., Vol. 42, Issue 4 https://doi.org/10.1039/c2cs35223k	journal	January 2013
Conductive two-dimensional metal–organic frameworks as multifunctional materials Ko, Michael; Mendecki, Lukasz; Mirica, Katherine A. Chemical Communications, Vol. 54, Issue 57 https://doi.org/10.1039/c8cc02871k	journal	January 2018
Increasing topological diversity during computational “synthesis” of porous crystals: how and why Anderson, Ryther; Gómez-Gualdrón, Diego A. CrystEngComm, Vol. 21, Issue 10 https://doi.org/10.1039/c8ce01637b	journal	January 2019
The role of photoinduced charge transfer for photocatalysis, photoelectrocatalysis and luminescence sensing in metal–organic frameworks Li, Xinlin; Surendran Rajasree, Sreehari; Yu, Jierui Dalton Transactions, Vol. 49, Issue 37 https://doi.org/10.1039/d0dt02143a	journal	January 2020
Control of dominant conduction orbitals by peripheral substituents in paddle-wheel diruthenium alkynyl molecular junctions Ogawa, Shiori; Chattopadhyay, Swarup; Tanaka, Yuya Chemical Science, Vol. 12, Issue 32 https://doi.org/10.1039/d1sc02407h	journal	January 2021
Natural transition orbitals Martin, Richard L. The Journal of Chemical Physics, Vol. 118, Issue 11 https://doi.org/10.1063/1.1558471	journal	March 2003
Reverse Monte Carlo modelling McGreevy, R. L. Journal of Physics: Condensed Matter, Vol. 13, Issue 46 https://doi.org/10.1088/0953-8984/13/46/201	journal	November 2001
A Chemically Functionalizable Nanoporous Material [Cu₃(TMA)₂(H₂O)₃]_n Chui, Stephen S.-Y.; Lo, Samuel M.-F.; Charmant, Jonathan P. H. Science, Vol. 283, Issue 5405, p. 1148-1150 https://doi.org/10.1126/science.283.5405.1148	journal	February 1999
Covalent organic frameworks comprising cobalt porphyrins for catalytic CO ₂ reduction in water Lin, Song; Diercks, Christian S.; Zhang, Yue-Biao Science, Vol. 349, Issue 6253 https://doi.org/10.1126/science.aac8343	journal	August 2015
Glotaran : A Java -Based Graphical User Interface for the R Package TIMP Snellenburg, Joris J.; Laptenok, Sergey P.; Seger, Ralf Journal of Statistical Software, Vol. 49, Issue 3 https://doi.org/10.18637/jss.v049.i03	journal	January 2012

Similar Records

Metal-Carbodithioate-Based 3D Semiconducting Metal-Organic Framework: Porous Optoelectronic Material for Energy Conversion

Journal Article · Wed May 31 00:00:00 EDT 2023 · ACS Applied Materials & Interfaces · OSTI ID:1986124

Mixed‐Valence Cu ^I /Cu ^III Metal–Organic Frameworks with Non‐innocent Ligand for Multielectron Transfer

Journal Article · Sun Sep 24 20:00:00 EDT 2023 · Angewandte Chemie · OSTI ID:2005008

Mixed‐Valence Cu ^I /Cu ^III Metal–Organic Frameworks with Non‐innocent Ligand for Multielectron Transfer

Journal Article · Sun Sep 24 20:00:00 EDT 2023 · Angewandte Chemie (International Edition) · OSTI ID:2005002

Related Subjects

36 MATERIALS SCIENCE
electrical conductivity
light-harvesting
materials
metal-carbodithioate linkae
metal-organic framework
photoelectrocatalysis
redox reactions
solvents
through-bond conductivity

Metal–Carbodithioate-Based 3D Semiconducting Metal–Organic Framework: Porous Optoelectronic Material for Energy Conversion

Citation Formats

References (56)

Similar Records

Related Subjects