Gold and Nickel Extended Thiophenic-TTF Bisdithiolene Complexes
Gold and nickel bisdithiolene complexes with methyl and tert-butyl substituted thiophenetetrathiafulavalenedithiolate ligands (α-mtdt and α-tbtdt) were prepared and characterized. These complexes were obtained, under anaerobic conditions, as tetrabutylammonium salts. The diamagnetic gold monoanion (...
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| Vydané v: | Molecules (Basel, Switzerland) Ročník 23; číslo 2; s. 424 |
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14.02.2018
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| Abstract | Gold and nickel bisdithiolene complexes with methyl and tert-butyl substituted thiophenetetrathiafulavalenedithiolate ligands (α-mtdt and α-tbtdt) were prepared and characterized. These complexes were obtained, under anaerobic conditions, as tetrabutylammonium salts. The diamagnetic gold monoanion (n-Bu4N)[Au(α-mtdt)2] (3) and nickel dianionic species (n-Bu4N)x[Ni(α-mtdt)2] (x = 1,2) (4) were similar to the related non-substituted extended thiophenic-TTF (TTF = tetrathiafulvalene) bisdithiolenes. However the introduction of the large, bulky substituent tert-butyl, led to the formation of a Au (I) dinuclear complex, (n-Bu4N)2[Au2(α-tbtdt)2] (5). The neutral methyl substituted gold and nickel complexes were easily obtained through air or iodine exposure as polycrystalline or amorphous fine powder. [Au(α-mtdt)2] (6) and [Ni(α-mtdt)2] (7) polycrystalline samples display properties of a metallic system with a room temperature electrical conductivity of 0.32 S/cm and ≈4 S/cm and a thermoelectric power of ≈5 µV/K and ≈32 µV/K, respectively. While [Au(α-mtdt)2] (6) presented a Pauli-like magnetic susceptibility typical of conducting systems, in [Ni(α-mtdt)2] (7) large magnetic susceptibilities indicative of high spin states were observed. Both electric transport properties and magnetic properties for gold and nickel [M(α-mtdt)2] are indicative that these compounds are single component molecular conductors. |
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| AbstractList | Gold and nickel bisdithiolene complexes with methyl and tert-butyl substituted thiophenetetrathiafulavalenedithiolate ligands (α-mtdt and α-tbtdt) were prepared and characterized. These complexes were obtained, under anaerobic conditions, as tetrabutylammonium salts. The diamagnetic gold monoanion (n-Bu4N)[Au(α-mtdt)2] (3) and nickel dianionic species (n-Bu4N)x[Ni(α-mtdt)2] (x = 1,2) (4) were similar to the related non-substituted extended thiophenic-TTF (TTF = tetrathiafulvalene) bisdithiolenes. However the introduction of the large, bulky substituent tert-butyl, led to the formation of a Au (I) dinuclear complex, (n-Bu4N)2[Au2(α-tbtdt)2] (5). The neutral methyl substituted gold and nickel complexes were easily obtained through air or iodine exposure as polycrystalline or amorphous fine powder. [Au(α-mtdt)2] (6) and [Ni(α-mtdt)2] (7) polycrystalline samples display properties of a metallic system with a room temperature electrical conductivity of 0.32 S/cm and ≈4 S/cm and a thermoelectric power of ≈5 µV/K and ≈32 µV/K, respectively. While [Au(α-mtdt)2] (6) presented a Pauli-like magnetic susceptibility typical of conducting systems, in [Ni(α-mtdt)2] (7) large magnetic susceptibilities indicative of high spin states were observed. Both electric transport properties and magnetic properties for gold and nickel [M(α-mtdt)2] are indicative that these compounds are single component molecular conductors. Gold and nickel bisdithiolene complexes with methyl and tert-butyl substituted thiophenetetrathiafulavalenedithiolate ligands (α-mtdt and α-tbtdt) were prepared and characterized. These complexes were obtained, under anaerobic conditions, as tetrabutylammonium salts. The diamagnetic gold monoanion (n-Bu₄N)[Au(α-mtdt)₂] (3) and nickel dianionic species (n-Bu₄N)x[Ni(α-mtdt)₂] (x = 1,2) (4) were similar to the related non-substituted extended thiophenic-TTF (TTF = tetrathiafulvalene) bisdithiolenes. However the introduction of the large, bulky substituent tert-butyl, led to the formation of a Au (I) dinuclear complex, (n-Bu₄N)₂[Au₂(α-tbtdt)₂] (5). The neutral methyl substituted gold and nickel complexes were easily obtained through air or iodine exposure as polycrystalline or amorphous fine powder. [Au(α-mtdt)₂] (6) and [Ni(α-mtdt)₂] (7) polycrystalline samples display properties of a metallic system with a room temperature electrical conductivity of 0.32 S/cm and ≈4 S/cm and a thermoelectric power of ≈5 µV/K and ≈32 µV/K, respectively. While [Au(α-mtdt)₂] (6) presented a Pauli-like magnetic susceptibility typical of conducting systems, in [Ni(α-mtdt)₂] (7) large magnetic susceptibilities indicative of high spin states were observed. Both electric transport properties and magnetic properties for gold and nickel [M(α-mtdt)₂] are indicative that these compounds are single component molecular conductors.Gold and nickel bisdithiolene complexes with methyl and tert-butyl substituted thiophenetetrathiafulavalenedithiolate ligands (α-mtdt and α-tbtdt) were prepared and characterized. These complexes were obtained, under anaerobic conditions, as tetrabutylammonium salts. The diamagnetic gold monoanion (n-Bu₄N)[Au(α-mtdt)₂] (3) and nickel dianionic species (n-Bu₄N)x[Ni(α-mtdt)₂] (x = 1,2) (4) were similar to the related non-substituted extended thiophenic-TTF (TTF = tetrathiafulvalene) bisdithiolenes. However the introduction of the large, bulky substituent tert-butyl, led to the formation of a Au (I) dinuclear complex, (n-Bu₄N)₂[Au₂(α-tbtdt)₂] (5). The neutral methyl substituted gold and nickel complexes were easily obtained through air or iodine exposure as polycrystalline or amorphous fine powder. [Au(α-mtdt)₂] (6) and [Ni(α-mtdt)₂] (7) polycrystalline samples display properties of a metallic system with a room temperature electrical conductivity of 0.32 S/cm and ≈4 S/cm and a thermoelectric power of ≈5 µV/K and ≈32 µV/K, respectively. While [Au(α-mtdt)₂] (6) presented a Pauli-like magnetic susceptibility typical of conducting systems, in [Ni(α-mtdt)₂] (7) large magnetic susceptibilities indicative of high spin states were observed. Both electric transport properties and magnetic properties for gold and nickel [M(α-mtdt)₂] are indicative that these compounds are single component molecular conductors. Gold and nickel bisdithiolene complexes with methyl and -butyl substituted thiophenetetrathiafulavalenedithiolate ligands (α-mtdt and α-tbtdt) were prepared and characterized. These complexes were obtained, under anaerobic conditions, as tetrabutylammonium salts. The diamagnetic gold monoanion ( -Bu₄N)[Au(α-mtdt)₂] ( ) and nickel dianionic species ( -Bu₄N) [Ni(α-mtdt)₂] (x = 1,2) ( ) were similar to the related non-substituted extended thiophenic-TTF (TTF = tetrathiafulvalene) bisdithiolenes. However the introduction of the large, bulky substituent -butyl, led to the formation of a Au (I) dinuclear complex, ( -Bu₄N)₂[Au₂(α-tbtdt)₂] ( ). The neutral methyl substituted gold and nickel complexes were easily obtained through air or iodine exposure as polycrystalline or amorphous fine powder. [Au(α-mtdt)₂] ( ) and [Ni(α-mtdt)₂] ( ) polycrystalline samples display properties of a metallic system with a room temperature electrical conductivity of 0.32 S/cm and ≈4 S/cm and a thermoelectric power of ≈5 µV/K and ≈32 µV/K, respectively. While [Au(α-mtdt)₂] ( ) presented a Pauli-like magnetic susceptibility typical of conducting systems, in [Ni(α-mtdt)₂] ( ) large magnetic susceptibilities indicative of high spin states were observed. Both electric transport properties and magnetic properties for gold and nickel [M(α-mtdt)₂] are indicative that these compounds are single component molecular conductors. |
| Author | Pereira, Laura Belo, Dulce Coutinho, Joana Almeida, Manuel Silva, Rafaela Santos, Isabel Vieira, Bruno Andrade, Marta Rabaça, Sandra Lopes, Elsa |
| AuthorAffiliation | C 2 TN, Centro de Ciências e Tecnologias Nucleares, Instituto Superior Técnico, Universidade de Lisboa, E.N. 10 ao km 139.7, 2695-066 Bobadela LRS, Portugal; rafaela@ctn.tecnico.ulisboa.pt (R.A.L.S.); brunovieira@ctn.tecnico.ulisboa.pt (B.J.C.V.); marta.m.s.andrade@gmail.com (M.M.A.); icsantos@ctn.tecnico.ulisboa.pt (I.C.S.); sandrar@ctn.tecnico.ulisboa.pt (S.R.); eblopes@ctn.tecnico.ulisboa.pt (E.B.L.); coutinho.joana@ctn.tecnico.ulisboa.pt (J.T.C.); lpereira@ctn.tecnico.ulisboa.pt (L.C.J.P.); malmeida@ctn.tecnico.ulisboa.pt (M.A.) |
| AuthorAffiliation_xml | – name: C 2 TN, Centro de Ciências e Tecnologias Nucleares, Instituto Superior Técnico, Universidade de Lisboa, E.N. 10 ao km 139.7, 2695-066 Bobadela LRS, Portugal; rafaela@ctn.tecnico.ulisboa.pt (R.A.L.S.); brunovieira@ctn.tecnico.ulisboa.pt (B.J.C.V.); marta.m.s.andrade@gmail.com (M.M.A.); icsantos@ctn.tecnico.ulisboa.pt (I.C.S.); sandrar@ctn.tecnico.ulisboa.pt (S.R.); eblopes@ctn.tecnico.ulisboa.pt (E.B.L.); coutinho.joana@ctn.tecnico.ulisboa.pt (J.T.C.); lpereira@ctn.tecnico.ulisboa.pt (L.C.J.P.); malmeida@ctn.tecnico.ulisboa.pt (M.A.) |
| Author_xml | – sequence: 1 givenname: Rafaela surname: Silva fullname: Silva, Rafaela – sequence: 2 givenname: Bruno surname: Vieira fullname: Vieira, Bruno – sequence: 3 givenname: Marta surname: Andrade fullname: Andrade, Marta – sequence: 4 givenname: Isabel orcidid: 0000-0001-8350-480X surname: Santos fullname: Santos, Isabel – sequence: 5 givenname: Sandra orcidid: 0000-0002-5324-8013 surname: Rabaça fullname: Rabaça, Sandra – sequence: 6 givenname: Elsa surname: Lopes fullname: Lopes, Elsa – sequence: 7 givenname: Joana surname: Coutinho fullname: Coutinho, Joana – sequence: 8 givenname: Laura orcidid: 0000-0002-8818-0039 surname: Pereira fullname: Pereira, Laura – sequence: 9 givenname: Manuel orcidid: 0000-0003-2222-5641 surname: Almeida fullname: Almeida, Manuel – sequence: 10 givenname: Dulce orcidid: 0000-0002-1571-6904 surname: Belo fullname: Belo, Dulce |
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| DOI | 10.3390/molecules23020424 |
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| Keywords | nickel bisdithiolene complexes gold bisdithiolene complexes thiophenetetrathiafulavalenedithiolate ligands single component molecular conductors |
| Language | English |
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| SubjectTerms | gold bisdithiolene complexes Nickel nickel bisdithiolene complexes single component molecular conductors thiophenetetrathiafulavalenedithiolate ligands |
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| Title | Gold and Nickel Extended Thiophenic-TTF Bisdithiolene Complexes |
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