Bis(Vinylenedithio)‐Tetrathiafulvalene‐Based Coordination Networks

• Published in: Chemistry : a European journal Vol. 29; no. 8; pp. e202203138 - n/a
• Main Authors: Solano, Federica, Auban‐Senzier, Pascale, Olejniczak, Iwona, Barszcz, Bolesław, Runka, Tomasz, Alemany, Pere, Canadell, Enric, Avarvari, Narcis, Zigon, Nicolas
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 07.02.2023; Wiley-VCH Verlag
• Subjects: Antiferromagnetism; Cadmium; Chemical Sciences; Chemistry; conducting materials; Conduction; Conductivity; Coordination chemistry; Coordination polymers; crystal engineering; Embedding; Iodine; Material chemistry; Mathematical analysis; metal-organic frameworks; Oxidation; Polymers; Porous materials; Raman spectroscopy; Sulfur; Transition metals; Valence; X-ray diffraction; X-ray diffraction; conducting materials; Raman spectroscopy; crystal engineering; metal-organic frameworks
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202203138

Novel coordination polymers embedding electroactive moieties present a high interest in the development of porous conducting materials. While tetrathiafulvalene (TTF) based metal‐organic frameworks were reported to yield through‐space conducting frameworks, the use of S‐enriched scaffolds remains elusive in this field. Herein is reported the employment of bis(vinylenedithio)‐tetrathiafulvalene (BVDT‐TTF) functionalized with pyridine coordinating moieties in coordination polymers. Its combination with various transition metals yielded four isostructural networks, whose conductivity increased upon chemical oxidation with iodine. The oxidation was confirmed in a single‐crystal to single‐crystal X‐ray diffraction experiment for the Cd(II) coordination polymer. Raman spectroscopy measurements and DFT calculations confirmed the oxidation state of the bulk materials, and band structure calculations assessed the ground state as an electronically localized antiferromagnetic state, while the conduction occurs in a 2D manner. These results are shedding light to comprehend how to improve through‐space conductivity thanks to sulfur enriched ligands. Sulphurous lateral interactions. For electroactive coordination polymers, through space charge transport phenomenon are most often 1D. By increasing the size of the electroactive core, lateral sulphur‐sulphur interaction take place and create a 2D conducting pathway. Post‐synthetic oxidation is used to increase the materials conductivity.