Synthesis of Conjugated Polymers by Coupling between Arenediazonium Tetrafluoroborates and Vinyl Silanes

Abstract

A new and general methodology for the synthesis of conjugated polymers presenting a variety of structural features is described. The methodology is based upon the palladiumcatalyzed coupling reaction of a bis(1-trimethylsilylethenyl)-benzene with arenebisdiazonium tetrafluoroborates.

Synthesis of (poly)gallic acid in a bacterial growth medium

“…[1][2][3] Soft conductive materials are often used as active films for interfacing the electrodes with the living cells or proteins. [4] Organic polyconjugated semiconductors [5][6][7][8] represent a valid option as conductive soft materials in biodevices. Among many conductive polymers, poly(gallic acid) (PGA) represents an interesting candidates as biocompatible interface for whole, living bacterial cells as its structure makes it quite adapt for interacting with the quinol/quinone moieties of several biomolecules.…”

Synthesis of (poly)gallic acid in a bacterial growth medium

“…[1][2][3] Soft conductive materials are often used as active films for interfacing the electrodes with the living cells or proteins. [4] Organic polyconjugated semiconductors [5][6][7][8] represent a valid option as conductive soft materials in biodevices. Among many conductive polymers, poly(gallic acid) (PGA) represents an interesting candidates as biocompatible interface for whole, living bacterial cells as its structure makes it quite adapt for interacting with the quinol/quinone moieties of several biomolecules.…”

A heptamethine cyanine dye suitable as antenna in biohybrids based on bacterial photosynthetic reaction center

“…This ability can be restored by chemically conjugating an organic fluorophore to the RC, forming a biohybrid. The concept of a functional biohybrid over performing the pristine protein in producing charge-separated state was firstly demonstrated using an aryleneethynylene fluorophore (AE 600 ) as artificial antenna [11][12][13][14]. A proper artificial antenna should (i) absorb in the visible region, (ii) possess an emission that overlaps the RC absorption for efficient energy transfer, (iii) possess a consistent Stokes shift for avoiding the self-absorption, (iv), have a high quantum yield and (v) have a chemical moiety suitable for RC anchoring.…”

“…The biohybrid AE 600 -RC fulfills all the above requisites and produces a fivefold increase in the amount of chargeseparated state compared to that obtained in pristine RC irradiated with the same number of photons having wavelength coincident with the maximum absorption of the dye. Several other dyes were synthesized according to previously published general procedure [14][15][16][17][18][19][20]. These molecules were used as artificial antennas both to a single wavelength [21][22][23][24] or under white light [25] and successfully used to enhance the photoactivity of the pristine RC.…”

Diazonium Salts as Substrates in Palladium-Catalyzed Cross-Coupling Reactions

“…Naso et al recently adapted the same methodology as reported for α-substituted vinylsilanes 70 to the stereoselective synthesis of distyryl benzenes 76 and synthesis of conjugated polymers 77 (Scheme ). As shown in Scheme , the present reactions were regio- and stereoselective and produced good yields of the final products.…”

“…Naso et al80a synthesized monodisperse poly(1,4-phenylenevinylene), PPV oligomers, using bromobenzenediazonium tetrafluoroborate as the key material in the elongation of the conjugate system (Scheme ).

36

…”

Synthesis of (poly)gallic acid in a bacterial growth medium

“…[1][2][3] Soft conductive materials are often used as active films for interfacing the electrodes with the living cells or proteins. [4] Organic polyconjugated semiconductors [5][6][7][8] represent a valid option as conductive soft materials in biodevices. Among many conductive polymers, poly(gallic acid) (PGA) represents an interesting candidates as biocompatible interface for whole, living bacterial cells as its structure makes it quite adapt for interacting with the quinol/quinone moieties of several biomolecules.…”

A heptamethine cyanine dye suitable as antenna in biohybrids based on bacterial photosynthetic reaction center

“…This ability can be restored by chemically conjugating an organic fluorophore to the RC, forming a biohybrid. The concept of a functional biohybrid over performing the pristine protein in producing charge-separated state was firstly demonstrated using an aryleneethynylene fluorophore (AE 600 ) as artificial antenna [11][12][13][14]. A proper artificial antenna should (i) absorb in the visible region, (ii) possess an emission that overlaps the RC absorption for efficient energy transfer, (iii) possess a consistent Stokes shift for avoiding the self-absorption, (iv), have a high quantum yield and (v) have a chemical moiety suitable for RC anchoring.…”

“…The biohybrid AE 600 -RC fulfills all the above requisites and produces a fivefold increase in the amount of chargeseparated state compared to that obtained in pristine RC irradiated with the same number of photons having wavelength coincident with the maximum absorption of the dye. Several other dyes were synthesized according to previously published general procedure [14][15][16][17][18][19][20]. These molecules were used as artificial antennas both to a single wavelength [21][22][23][24] or under white light [25] and successfully used to enhance the photoactivity of the pristine RC.…”

Diazonium Salts as Substrates in Palladium-Catalyzed Cross-Coupling Reactions

“…Naso et al recently adapted the same methodology as reported for α-substituted vinylsilanes 70 to the stereoselective synthesis of distyryl benzenes 76 and synthesis of conjugated polymers 77 (Scheme ). As shown in Scheme , the present reactions were regio- and stereoselective and produced good yields of the final products.…”

“…Naso et al80a synthesized monodisperse poly(1,4-phenylenevinylene), PPV oligomers, using bromobenzenediazonium tetrafluoroborate as the key material in the elongation of the conjugate system (Scheme ).

36

…”

Synthesis of (poly)gallic acid in a bacterial growth medium

“…[1][2][3] Soft conductive materials are often used as active films for interfacing the electrodes with the living cells or proteins. [4] Organic polyconjugated semiconductors [5][6][7][8] represent a valid option as conductive soft materials in biodevices. Among many conductive polymers, poly(gallic acid) (PGA) represents an interesting candidates as biocompatible interface for whole, living bacterial cells as its structure makes it quite adapt for interacting with the quinol/quinone moieties of several biomolecules.…”

A heptamethine cyanine dye suitable as antenna in biohybrids based on bacterial photosynthetic reaction center

“…This ability can be restored by chemically conjugating an organic fluorophore to the RC, forming a biohybrid. The concept of a functional biohybrid over performing the pristine protein in producing charge-separated state was firstly demonstrated using an aryleneethynylene fluorophore (AE 600 ) as artificial antenna [11][12][13][14]. A proper artificial antenna should (i) absorb in the visible region, (ii) possess an emission that overlaps the RC absorption for efficient energy transfer, (iii) possess a consistent Stokes shift for avoiding the self-absorption, (iv), have a high quantum yield and (v) have a chemical moiety suitable for RC anchoring.…”

“…The biohybrid AE 600 -RC fulfills all the above requisites and produces a fivefold increase in the amount of chargeseparated state compared to that obtained in pristine RC irradiated with the same number of photons having wavelength coincident with the maximum absorption of the dye. Several other dyes were synthesized according to previously published general procedure [14][15][16][17][18][19][20]. These molecules were used as artificial antennas both to a single wavelength [21][22][23][24] or under white light [25] and successfully used to enhance the photoactivity of the pristine RC.…”

Diazonium Salts as Substrates in Palladium-Catalyzed Cross-Coupling Reactions

“…Naso et al recently adapted the same methodology as reported for α-substituted vinylsilanes 70 to the stereoselective synthesis of distyryl benzenes 76 and synthesis of conjugated polymers 77 (Scheme ). As shown in Scheme , the present reactions were regio- and stereoselective and produced good yields of the final products.…”

“…Naso et al80a synthesized monodisperse poly(1,4-phenylenevinylene), PPV oligomers, using bromobenzenediazonium tetrafluoroborate as the key material in the elongation of the conjugate system (Scheme ).

36

…”