Crystal Structures and Electrical Resistivity of Three Exotic TMTSF Salts with I3-: Determination of Valence by DFT and MP2 Calculations

• Main Authors: Harukazu Yoshino, Yoshiki Iwasaki, Rika Tanaka, Yuka Tsujimoto, Chiaki Matsuoka
• Format: Article
• Language: English
• Published: MDPI AG 2020-12-01
• Series: Crystals
• Subjects: (TMTSF)8(I3)5; (TMTSF)5(I3)2; (TMTSF)4(I3)4·THF; organic conductor; crystal structure; electrical resistivity
• Online Access: https://www.mdpi.com/2073-4352/10/12/1119

Three novel organic conductors (TMTSF)<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>8</mn></msub></semantics></math></inline-formula>(I<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>3</mn></msub></semantics></math></inline-formula>)<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>5</mn></msub></semantics></math></inline-formula>, (TMTSF)<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>5</mn></msub></semantics></math></inline-formula>(I<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>3</mn></msub></semantics></math></inline-formula>)<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>, and (TMTSF)<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>4</mn></msub></semantics></math></inline-formula>(I<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>3</mn></msub></semantics></math></inline-formula>)<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>4</mn></msub></semantics></math></inline-formula>·THF (THF = tetrahydrofuran) were synthesized and their crystal structures were characterized by X-ray diffraction analyses, where TMTSF denotes tetramethyltetraselenafulvalene. The crystals of both the (TMTSF)<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>8</mn></msub></semantics></math></inline-formula>(I<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>3</mn></msub></semantics></math></inline-formula>)<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>5</mn></msub></semantics></math></inline-formula> and (TMTSF)<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>5</mn></msub></semantics></math></inline-formula>(I<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>3</mn></msub></semantics></math></inline-formula>)<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula> are composed of one-dimensional stacks of TMTSF trimers separated by TMTSF monomers. The crystal of the (TMTSF)<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>4</mn></msub></semantics></math></inline-formula>(I<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>3</mn></msub></semantics></math></inline-formula>)<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>4</mn></msub></semantics></math></inline-formula>·THF is composed of the TMTSF tetramers and I<inline-formula><math display="inline"><semantics><msubsup><mrow></mrow><mn>3</mn><mo>−</mo></msubsup></semantics></math></inline-formula> tetramers; and regarded as the elongated rock-salt structure. The electrical conductivity of the (TMTSF)<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>8</mn></msub></semantics></math></inline-formula>(I<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>3</mn></msub></semantics></math></inline-formula>)<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>5</mn></msub></semantics></math></inline-formula> and (TMTSF)<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>5</mn></msub></semantics></math></inline-formula>(I<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>3</mn></msub></semantics></math></inline-formula>)<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula> is about 60 and 50 S·cm<inline-formula><math display="inline"><semantics><msup><mrow></mrow><mrow><mo>−</mo><mn>1</mn></mrow></msup></semantics></math></inline-formula> at room temperature, respectively. The electrical resistivity of (TMTSF)<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>8</mn></msub></semantics></math></inline-formula>(I<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>3</mn></msub></semantics></math></inline-formula>)<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>5</mn></msub></semantics></math></inline-formula> is weakly metallic below room temperature and rapidly increases below 88 and 53 K on cooling suggesting two possible phase transitions. The electrical resistivity of (TMTSF)<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>5</mn></msub></semantics></math></inline-formula>(I<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>3</mn></msub></semantics></math></inline-formula>)<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula> is semiconducting below room temperature but shows an anomaly around 190 K, below which the activation energy becomes small. The application of hydrostatic pressure up to 1.7 GPa do not change these behaviors of (TMTSF)<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>8</mn></msub></semantics></math></inline-formula>(I<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>3</mn></msub></semantics></math></inline-formula>)<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>5</mn></msub></semantics></math></inline-formula> and (TMTSF)<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>5</mn></msub></semantics></math></inline-formula>(I<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>3</mn></msub></semantics></math></inline-formula>)<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula> very much. A method to evaluate the non-integer valence of crystallographically independent TMTSF molecules is developed by using the DFT (density-functional-theory) and MP2 (Hartree–Fock calculations followed by Møller–Plesset correlation energy calculations truncated at second order) calculations. It is shown that the method gives the valence of the TMTSF molecules of the I<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>3</mn></msub></semantics></math></inline-formula> salts consistent with their electrical properties.