Trimethyltetrathiafulvalene Bearing anN-Methylpyridinium Substituent: Synthesis, Crystal Structures, and Charge Transfer Properties

Abstract

The synthesis of 4,4Ј,5-trimethyl-5Ј-(4-pyridyl)tetrathiafulvalene (3), has been accomplished by reaction of the stannylated precursor 2 with 4-bromopyridine. Alkylation of 3 affords the N-methylpyridinium salt 4 which displays intramolecular charge transfer properties in solution as deduced from UV/Vis spectra, cyclic voltammetric data, and semiempirical quantum mechanical calculations. The X-ray crystal structures of neutral molecule 3, the salt (4 + )I − and the charge

W6S8 Inorganic Clusters with Organic TTF Derivative Ligands: in Pursuit of Multidimensional Conductive Networks

“…It is therefore in large part the interplay of these two factors that defines our further experimental pursuits. With the well-established synthesis work on various TTF derivatives [71][72][73] as well as on other potentially interesting organic ligands, [74][75][76][77] we believe the reported work herein also opens up access to a wide variety of multifunctional molecular materials.…”

W6S8 Inorganic Clusters with Organic TTF Derivative Ligands: in Pursuit of Multidimensional Conductive Networks

“…It is therefore in large part the interplay of these two factors that defines our further experimental pursuits. With the well-established synthesis work on various TTF derivatives [71][72][73] as well as on other potentially interesting organic ligands, [74][75][76][77] we believe the reported work herein also opens up access to a wide variety of multifunctional molecular materials.…”

Preparation and Crystal Structure of Dual-Functional Precursor Complex Bis(acetylacetonato)nickel(II) with 4-Pyridyltetrathiafulvalene

“…Synthesis of Py-TTF. There are two kinds of available reactions to result in Py-TTF derivatives; , we select the use of the organometallic strategy described by Iyoda co-workers because it obtained 4,4‘,5-trimethyl-5‘-pyridyltetrathiafulvalene in good yield and recently proved to be successful for a series of heterocyclic aromatic-substituted TTF derivatives . The synthesis of target Py-TTF is shown in Scheme with good yield (46%), which is higher than the reported one …”

Tetrathiafulvalene-based group XV ligands: Synthesis, coordination chemistry and radical cation salts

“…The same synthetic procedure involving TTF-SnR 3 has been used with 2,6-dibromopyridine [11] or 4-bromopyridine as reactants [12]. N-methylation afforded for example the corresponding N-methyl-4-pyridinium-TTF, a TTF-A diad molecule (A = electron acceptor moiety) exhibiting intramolecular charge transfer (ICT).…”

“…The mono and bis-pyridyl-TTFs can also be prepared from the unsymmetrical or symmetrical coupling using the 4-pyridyl-1,3-dithiole-2-one in the presence of neat triethylphosphite but in rather low yields [16][17][18]. The pyridine substituent directly linked to the donor core has no significant electron withdrawing effect on the redox properties of the donor core as the oxidation potentials remain very close to those of the non-substituted TTFs [10][11][12][13][14][15][16][17] (Table 1).…”

“…As soon as the oxidation is conducted with more than one equivalent of chemical oxidant, e.g. AgClO 4 , or at a potential higher than the one required for the second oxidation of the compound, the typical heptuplet signal for the free [ The unique TTF-phosphine-based ruthenium complex (Ru9) reported so far contains the diphosphine 104 coordinated to the Ru(CO) 3 fragment and was prepared from the precursor Ru 3 (CO) 12 (Scheme 45) [112]. Its structure, ascertained by single crystal X-ray study, shows a metal center in a slightly distorted trigonal bipyramid environment, with a planar 5-member ring metallacycle, as well as essentially planar dithiole halves (Fig.…”

W6S8 Inorganic Clusters with Organic TTF Derivative Ligands: in Pursuit of Multidimensional Conductive Networks

“…It is therefore in large part the interplay of these two factors that defines our further experimental pursuits. With the well-established synthesis work on various TTF derivatives [71][72][73] as well as on other potentially interesting organic ligands, [74][75][76][77] we believe the reported work herein also opens up access to a wide variety of multifunctional molecular materials.…”

Preparation and Crystal Structure of Dual-Functional Precursor Complex Bis(acetylacetonato)nickel(II) with 4-Pyridyltetrathiafulvalene

“…Synthesis of Py-TTF. There are two kinds of available reactions to result in Py-TTF derivatives; , we select the use of the organometallic strategy described by Iyoda co-workers because it obtained 4,4‘,5-trimethyl-5‘-pyridyltetrathiafulvalene in good yield and recently proved to be successful for a series of heterocyclic aromatic-substituted TTF derivatives . The synthesis of target Py-TTF is shown in Scheme with good yield (46%), which is higher than the reported one …”

Tetrathiafulvalene-based group XV ligands: Synthesis, coordination chemistry and radical cation salts

“…The same synthetic procedure involving TTF-SnR 3 has been used with 2,6-dibromopyridine [11] or 4-bromopyridine as reactants [12]. N-methylation afforded for example the corresponding N-methyl-4-pyridinium-TTF, a TTF-A diad molecule (A = electron acceptor moiety) exhibiting intramolecular charge transfer (ICT).…”

“…The mono and bis-pyridyl-TTFs can also be prepared from the unsymmetrical or symmetrical coupling using the 4-pyridyl-1,3-dithiole-2-one in the presence of neat triethylphosphite but in rather low yields [16][17][18]. The pyridine substituent directly linked to the donor core has no significant electron withdrawing effect on the redox properties of the donor core as the oxidation potentials remain very close to those of the non-substituted TTFs [10][11][12][13][14][15][16][17] (Table 1).…”

“…As soon as the oxidation is conducted with more than one equivalent of chemical oxidant, e.g. AgClO 4 , or at a potential higher than the one required for the second oxidation of the compound, the typical heptuplet signal for the free [ The unique TTF-phosphine-based ruthenium complex (Ru9) reported so far contains the diphosphine 104 coordinated to the Ru(CO) 3 fragment and was prepared from the precursor Ru 3 (CO) 12 (Scheme 45) [112]. Its structure, ascertained by single crystal X-ray study, shows a metal center in a slightly distorted trigonal bipyramid environment, with a planar 5-member ring metallacycle, as well as essentially planar dithiole halves (Fig.…”

W6S8 Inorganic Clusters with Organic TTF Derivative Ligands: in Pursuit of Multidimensional Conductive Networks

“…It is therefore in large part the interplay of these two factors that defines our further experimental pursuits. With the well-established synthesis work on various TTF derivatives [71][72][73] as well as on other potentially interesting organic ligands, [74][75][76][77] we believe the reported work herein also opens up access to a wide variety of multifunctional molecular materials.…”

Preparation and Crystal Structure of Dual-Functional Precursor Complex Bis(acetylacetonato)nickel(II) with 4-Pyridyltetrathiafulvalene

“…Synthesis of Py-TTF. There are two kinds of available reactions to result in Py-TTF derivatives; , we select the use of the organometallic strategy described by Iyoda co-workers because it obtained 4,4‘,5-trimethyl-5‘-pyridyltetrathiafulvalene in good yield and recently proved to be successful for a series of heterocyclic aromatic-substituted TTF derivatives . The synthesis of target Py-TTF is shown in Scheme with good yield (46%), which is higher than the reported one …”

Tetrathiafulvalene-based group XV ligands: Synthesis, coordination chemistry and radical cation salts

“…The same synthetic procedure involving TTF-SnR 3 has been used with 2,6-dibromopyridine [11] or 4-bromopyridine as reactants [12]. N-methylation afforded for example the corresponding N-methyl-4-pyridinium-TTF, a TTF-A diad molecule (A = electron acceptor moiety) exhibiting intramolecular charge transfer (ICT).…”

“…The mono and bis-pyridyl-TTFs can also be prepared from the unsymmetrical or symmetrical coupling using the 4-pyridyl-1,3-dithiole-2-one in the presence of neat triethylphosphite but in rather low yields [16][17][18]. The pyridine substituent directly linked to the donor core has no significant electron withdrawing effect on the redox properties of the donor core as the oxidation potentials remain very close to those of the non-substituted TTFs [10][11][12][13][14][15][16][17] (Table 1).…”

“…As soon as the oxidation is conducted with more than one equivalent of chemical oxidant, e.g. AgClO 4 , or at a potential higher than the one required for the second oxidation of the compound, the typical heptuplet signal for the free [ The unique TTF-phosphine-based ruthenium complex (Ru9) reported so far contains the diphosphine 104 coordinated to the Ru(CO) 3 fragment and was prepared from the precursor Ru 3 (CO) 12 (Scheme 45) [112]. Its structure, ascertained by single crystal X-ray study, shows a metal center in a slightly distorted trigonal bipyramid environment, with a planar 5-member ring metallacycle, as well as essentially planar dithiole halves (Fig.…”