{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,29]],"date-time":"2026-09-29T18:34:48Z","timestamp":1790706888772,"version":"4.1.0"},"reference-count":37,"publisher":"Frontiers Media SA","license":[{"start":{"date-parts":[[2021,10,1]],"date-time":"2021-10-01T00:00:00Z","timestamp":1633046400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["1809092 1660329"],"award-info":[{"award-number":["1809092 1660329"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["frontiersin.org"],"crossmark-restriction":true},"short-container-title":["Front. Chem."],"abstract":"<jats:p>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 <jats:italic>cis<\/jats:italic>-dipyridyl-tetrathiafulvalene (<jats:italic>Z<\/jats:italic>-DPTTF) ligand. While TCPB formed Zn<jats:sub>2<\/jats:sub>(COO)<jats:sub>4<\/jats:sub> secondary building units (SBUs), instead of connecting the Zn<jats:sub>2<\/jats:sub>-paddlewheel SBUs located in different planes and forming a traditional pillared paddlewheel MOF, the U-shaped <jats:italic>Z<\/jats:italic>-DPTTF ligands bridged the neighboring SBUs formed by the same TCPB ligand like a sine-curve along the b axis that created a new <jats:italic>sine<\/jats:italic>-MOF architecture. The pristine <jats:italic>sine<\/jats:italic>-MOF displayed an intrinsic electrical conductivity of 1 \u00d7 10<jats:sup>\u22128<\/jats:sup>\u00a0S\/m, which surged to 5 \u00d7 10<jats:sup>\u22127<\/jats:sup>\u00a0S\/m after I<jats:sub>2<\/jats:sub> doping due to partial oxidation of electron rich <jats:italic>Z<\/jats:italic>-DPTTF ligands that raised the charge-carrier concentration inside the framework. However, the conductivities of the pristine and I<jats:sub>2<\/jats:sub>-treated <jats:italic>sine<\/jats:italic>-MOFs were modest possibly because of large spatial distances between the ligands that prevented \u03c0-donor\/acceptor charge-transfer interactions needed for effective through-space charge movement in 3D MOFs that lack through coordination-bond charge transport pathways.<\/jats:p>","DOI":"10.3389\/fchem.2021.726544","type":"journal-article","created":{"date-parts":[[2021,10,1]],"date-time":"2021-10-01T09:58:32Z","timestamp":1633082312000},"update-policy":"https:\/\/doi.org\/10.3389\/crossmark-policy","source":"Crossref","is-referenced-by-count":9,"title":["A New Electrically Conducting Metal\u2013Organic Framework Featuring U-Shaped cis-Dipyridyl Tetrathiafulvalene Ligands"],"prefix":"10.3389","volume":"9","author":[{"given":"Monica A.","family":"Gordillo","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Paola A.","family":"Benavides","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kaybriana","family":"Spalding","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sourav","family":"Saha","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1965","published-online":{"date-parts":[[2021,10,1]]},"reference":[{"key":"B1","doi-asserted-by":"publisher","first-page":"2245","DOI":"10.1039\/b818607n","article-title":"Tetrathiafulvalene (TTF) Derivatives: Key Building-Blocks for Switchable Processes","volume":"17","author":"Canevet","year":"2009","journal-title":"Chem. Commun."},{"key":"B2","doi-asserted-by":"publisher","first-page":"8957","DOI":"10.1039\/C6CC00805D","article-title":"Exploiting Redox Activity in Metal-Organic Frameworks: Concepts, Trends and Perspectives","volume":"52","author":"D'Alessandro","year":"2016","journal-title":"Chem. Commun."},{"key":"B3","doi-asserted-by":"publisher","first-page":"213891","DOI":"10.1016\/j.ccr.2021.213891","article-title":"Redox-active Ligands: Recent Advances towards Their Incorporation into Coordination Polymers and Metal-Organic Frameworks","volume":"439","author":"Ding","year":"2021","journal-title":"Coord. Chem. Rev."},{"key":"B4","doi-asserted-by":"publisher","first-page":"890","DOI":"10.1557\/mrs.2016.246","article-title":"Metal-organic Framework Photophysics: Optoelectronic Devices, Photoswitches, Sensors, and Photocatalysts","volume":"41","author":"Dolgopolova","year":"2016","journal-title":"MRS Bull."},{"key":"B5","doi-asserted-by":"publisher","first-page":"974","DOI":"10.1126\/science.1230444","article-title":"The Chemistry and Applications of Metal-Organic Frameworks","volume":"341","author":"Furukawa","year":"2013","journal-title":"Science"},{"key":"B6","doi-asserted-by":"publisher","first-page":"5321","DOI":"10.1021\/ic5006117","article-title":"Stabilizing Radical Cation and Dication of a Tetrathiafulvalene Derivative by a Weakly Coordinating Anion","volume":"53","author":"Gao","year":"2014","journal-title":"Inorg. Chem."},{"key":"B7","doi-asserted-by":"publisher","first-page":"12955","DOI":"10.1021\/acsami.9b20234","article-title":"The Advent of Electrically Conducting Double-Helical Metal-Organic Frameworks Featuring Butterfly-Shaped Electron-Rich \u03c0-Extended Tetrathiafulvalene Ligands","volume":"12","author":"Gordillo","year":"2020","journal-title":"ACS Appl. Mater. Inter."},{"key":"B8","doi-asserted-by":"publisher","first-page":"3196","DOI":"10.1021\/acsami.8b17807","article-title":"Efficient MOF-Sensitized Solar Cells Featuring Solvothermally Grown [100]-Oriented Pillared Porphyrin Framework-11 Films on ZnO\/FTO Surfaces","volume":"11","author":"Gordillo","year":"2019","journal-title":"ACS Appl. Mater. Inter."},{"key":"B9","doi-asserted-by":"publisher","first-page":"4545","DOI":"10.1016\/j.jorganchem.2007.04.034","article-title":"Synthesis and Characterization of Half-sandwich Iridium Complexes Containing 2,6(7)-Bis(4-Pyridyl)-1,4,5,8-Tetrathiafulvalene and Ancillary Ortho-Carborane-1,2-Dichalcogenolato Ligands","volume":"692","author":"Han","year":"2007","journal-title":"J. Organomet. Chem."},{"key":"B10","doi-asserted-by":"publisher","first-page":"2376","DOI":"10.1021\/ar300291s","article-title":"Ion Conductivity and Transport by Porous Coordination Polymers and Metal-Organic Frameworks","volume":"46","author":"Horike","year":"2013","journal-title":"Acc. Chem. Res."},{"key":"B11","doi-asserted-by":"publisher","first-page":"12707","DOI":"10.1021\/acs.inorgchem.9b01595","article-title":"Thiazolothiazole-Based Luminescent Metal-Organic Frameworks with Ligand-To-Ligand Energy Transfer and Hg2+-Sensing Capabilities","volume":"58","author":"Khatun","year":"2019","journal-title":"Inorg. Chem."},{"key":"B12","doi-asserted-by":"publisher","first-page":"334","DOI":"10.1016\/J.POLY.2018.07.023","article-title":"A Spectroscopic and Electrochemical Investigation of a Tetrathiafulvalene Series of Metal-Organic Frameworks","volume":"154","author":"Leong","year":"2018","journal-title":"Polyhedron"},{"key":"B13","doi-asserted-by":"publisher","first-page":"869","DOI":"10.1021\/cr200190s","article-title":"Metal-Organic Frameworks for Separations","volume":"112","author":"Li","year":"2012","journal-title":"Chem. Rev."},{"key":"B14","doi-asserted-by":"publisher","first-page":"6011","DOI":"10.1039\/C4CS00094C","article-title":"Applications of Metal-Organic Frameworks in Heterogeneous Supramolecular Catalysis","volume":"43","author":"Liu","year":"2014","journal-title":"Chem. Soc. Rev."},{"key":"B15","doi-asserted-by":"publisher","first-page":"7441","DOI":"10.1002\/anie.201501862","article-title":"Photoinduced Charge-Carrier Generation in Epitaxial MOF Thin Films: High Efficiency as a Result of an Indirect Electronic Band Gap?","volume":"54","author":"Liu","year":"2015","journal-title":"Angew. Chem. Int. Ed."},{"key":"B16","doi-asserted-by":"publisher","first-page":"3242","DOI":"10.1039\/C6CS00930A","article-title":"Metal-organic Frameworks: Functional Luminescent and Photonic Materials for Sensing Applications","volume":"46","author":"Lustig","year":"2017","journal-title":"Chem. Soc. Rev."},{"key":"B17","doi-asserted-by":"publisher","first-page":"719","DOI":"10.1039\/c5sc01565k","article-title":"Ruthenium(II)-polypyridyl Zirconium(IV) Metal-Organic Frameworks as a New Class of Sensitized Solar Cells","volume":"7","author":"Maza","year":"2016","journal-title":"Chem. Sci."},{"key":"B18","doi-asserted-by":"publisher","first-page":"12932","DOI":"10.1021\/ja3059827","article-title":"High Charge Mobility in a Tetrathiafulvalene-Based Microporous Metal-Organic Framework","volume":"134","author":"Narayan","year":"2012","journal-title":"J. Am. Chem. Soc."},{"key":"B19","doi-asserted-by":"publisher","first-page":"1774","DOI":"10.1021\/ja512437u","article-title":"Cation-Dependent Intrinsic Electrical Conductivity in Isostructural Tetrathiafulvalene-Based Microporous Metal-Organic Frameworks","volume":"137","author":"Park","year":"2015","journal-title":"J. Am. Chem. Soc."},{"key":"B20","doi-asserted-by":"publisher","first-page":"5913","DOI":"10.1039\/C4CS00093E","article-title":"MOFs as Proton Conductors - Challenges and Opportunities","volume":"43","author":"Ramaswamy","year":"2014","journal-title":"Chem. Soc. Rev."},{"key":"B21","doi-asserted-by":"publisher","first-page":"8790","DOI":"10.1021\/acs.chemrev.9b00350","article-title":"Photophysics Modulation in Photoswitchable Metal-Organic Frameworks","volume":"120","author":"Rice","year":"2020","journal-title":"Chem. Rev."},{"key":"B22","doi-asserted-by":"publisher","first-page":"1372","DOI":"10.1002\/1521-3773(20010417)40:8<1372:AID-ANIE1372>3.0.CO;2-I","article-title":"New Concepts in Tetrathiafulvalene Chemistry","volume":"40","author":"Segura","year":"2001","journal-title":"Angew. Chem. Int. Ed."},{"key":"B23","doi-asserted-by":"publisher","first-page":"1","DOI":"10.1038\/s41467-020-15510-7","article-title":"Reversible Single crystal-to-single crystal Double [2+2] Cycloaddition Induces Multifunctional Photo-Mechano-Electrochemical Properties in Framework Materials","volume":"11","author":"Sherman","year":"2020","journal-title":"Nat. Commun."},{"key":"B24","doi-asserted-by":"publisher","first-page":"3501","DOI":"10.1039\/C4CC09596K","article-title":"Metal-organic Framework Materials for Light-Harvesting and Energy Transfer","volume":"51","author":"So","year":"2015","journal-title":"Chem. Commun."},{"key":"B25","doi-asserted-by":"publisher","first-page":"3185","DOI":"10.1039\/C7CS00122C","article-title":"An Updated Roadmap for the Integration of Metal-Organic Frameworks with Electronic Devices and Chemical Sensors","volume":"46","author":"Stassen","year":"2017","journal-title":"Chem. Soc. Rev."},{"key":"B26","doi-asserted-by":"publisher","first-page":"5994","DOI":"10.1039\/C4CS00096J","article-title":"MOF-based Electronic and Opto-Electronic Devices","volume":"43","author":"Stavila","year":"2014","journal-title":"Chem. Soc. Rev."},{"key":"B27","doi-asserted-by":"publisher","first-page":"1","DOI":"10.1038\/s41467-017-02256-y","article-title":"Redox-switchable Breathing Behavior in Tetrathiafulvalene-Based Metal-Organic Frameworks","volume":"8","author":"Su","year":"2017","journal-title":"Nat. Commun."},{"key":"B28","doi-asserted-by":"publisher","first-page":"724","DOI":"10.1021\/cr2003272","article-title":"Carbon Dioxide Capture in Metal-Organic Frameworks","volume":"112","author":"Sumida","year":"2012","journal-title":"Chem. Rev."},{"key":"B29","doi-asserted-by":"publisher","first-page":"3566","DOI":"10.1002\/anie.201506219","article-title":"Electrically Conductive Porous Metal-Organic Frameworks","volume":"55","author":"Sun","year":"2016","journal-title":"Angew. Chem. Int. Ed."},{"key":"B30","doi-asserted-by":"publisher","first-page":"342","DOI":"10.1016\/j.ccr.2016.10.011","article-title":"Functional Coordination Polymers Based on Redox-Active Tetrathiafulvalene and its Derivatives","volume":"345","author":"Wang","year":"","journal-title":"Coord. Chem. Rev."},{"key":"B33","doi-asserted-by":"publisher","first-page":"5465","DOI":"10.1002\/anie.201611824","article-title":"Photo\u2010 and Electronically Switchable Spin\u2010Crossover Iron(II) Metal-Organic Frameworks Based on a Tetrathiafulvalene Ligand","volume":"56","author":"Wang","year":"","journal-title":"Angew. Chem. Int. Ed."},{"key":"B31","doi-asserted-by":"publisher","first-page":"8657","DOI":"10.1021\/acs.inorgchem.9b01000","article-title":"Concomitant Use of Tetrathiafulvalene and 7,7,8,8-Tetracyanoquinodimethane within the Skeletons of Metal-Organic Frameworks: Structures, Magnetism, and Electrochemistry","volume":"58","author":"Wang","year":"2019","journal-title":"Inorg. Chem."},{"key":"B32","doi-asserted-by":"publisher","first-page":"10766","DOI":"10.1021\/acs.inorgchem.5b01803","article-title":"Crystal Structures, Magnetic Properties, and Electrochemical Properties of Coordination Polymers Based on the Tetra(4-Pyridyl)-Tetrathiafulvalene Ligand","volume":"54","author":"Wang","year":"2015","journal-title":"Inorg. Chem."},{"key":"B34","doi-asserted-by":"publisher","first-page":"52615","DOI":"10.1021\/acsami.0c14510","article-title":"Tetrathiafulvalene-Based Metal-Organic Framework as a High-Performance Anode for Lithium-Ion Batteries","volume":"12","author":"Weng","year":"2020","journal-title":"ACS Appl. Mater. Inter."},{"key":"B35","doi-asserted-by":"publisher","first-page":"9154","DOI":"10.1021\/acs.inorgchem.6b01632","article-title":"3D Copper Tetrathiafulvalene Redox-Active Network with 8-fold Interpenetrating diamond-like Topology","volume":"55","author":"Yin","year":"2016","journal-title":"Inorg. Chem."},{"key":"B36","doi-asserted-by":"publisher","DOI":"10.1002\/adma.201704303","article-title":"Stable Metal-Organic Frameworks: Design, Synthesis, and Applications","volume":"30","author":"Yuan","year":"2018","journal-title":"Adv. Mater."},{"key":"B37","doi-asserted-by":"publisher","first-page":"5982","DOI":"10.1039\/C4CS00103F","article-title":"Metal-organic Frameworks for Artificial Photosynthesis and Photocatalysis","volume":"43","author":"Zhang","year":"2014","journal-title":"Chem. Soc. Rev."}],"container-title":["Frontiers in Chemistry"],"original-title":[],"link":[{"URL":"https:\/\/www.frontiersin.org\/articles\/10.3389\/fchem.2021.726544\/full","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2021,10,1]],"date-time":"2021-10-01T09:58:35Z","timestamp":1633082315000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.frontiersin.org\/articles\/10.3389\/fchem.2021.726544\/full"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2021,10,1]]},"references-count":37,"alternative-id":["10.3389\/fchem.2021.726544"],"URL":"https:\/\/doi.org\/10.3389\/fchem.2021.726544","relation":{},"ISSN":["2296-2646"],"issn-type":[{"value":"2296-2646","type":"electronic"}],"subject":[],"published":{"date-parts":[[2021,10,1]]},"article-number":"726544"}}