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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Vydáno v:Molecules (Basel, Switzerland) Ročník 23; číslo 2; s. 424
Hlavní autoři: Silva, Rafaela, Vieira, Bruno, Andrade, Marta, Santos, Isabel, Rabaça, Sandra, Lopes, Elsa, Coutinho, Joana, Pereira, Laura, Almeida, Manuel, Belo, Dulce
Médium: Journal Article
Jazyk:angličtina
Vydáno: Switzerland MDPI AG 14.02.2018
MDPI
Témata:
gold bisdithiolene complexes
Nickel
nickel bisdithiolene complexes
single component molecular conductors
thiophenetetrathiafulavalenedithiolate ligands
nickel bisdithiolene complexes
gold bisdithiolene complexes
thiophenetetrathiafulavalenedithiolate ligands
single component molecular conductors
ISSN:1420-3049, 1420-3049
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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.
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.)
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crossref_primary_10_3390_cryst11070838
crossref_primary_10_3390_inorganics8100053
crossref_primary_10_3390_molecules23020424
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Issue 2
Keywords nickel bisdithiolene complexes
gold bisdithiolene complexes
thiophenetetrathiafulavalenedithiolate ligands
single component molecular conductors
Language English
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Snippet Gold and nickel bisdithiolene complexes with methyl and tert-butyl substituted thiophenetetrathiafulavalenedithiolate ligands (α-mtdt and α-tbtdt) were...
Gold and nickel bisdithiolene complexes with methyl and -butyl substituted thiophenetetrathiafulavalenedithiolate ligands (α-mtdt and α-tbtdt) were prepared...
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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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