Challenges and Advances in Computational Chemistry and Physics, 2006
ABSTRACT Boron-subphthalocyanines (SubPcs)—cone-shaped 14-π electron aromatic macrocycles—are low... more ABSTRACT Boron-subphthalocyanines (SubPcs)—cone-shaped 14-π electron aromatic macrocycles—are lower phthalocyanine analogues which consist of three isoindole units N-fused around a central boron atom which fourth valency is occupied by an axial ligand. SubPcs have been shown to possess very interesting features for NLO. Although they present a permanent dipole moment along the boron-axial substituent axis, their optical response is essentially associated to charge transfer inside the macrocycle π-surface. Moreover, due to the C3v symmetry of the SubPc core, its NLO behavior is mostly octupolar. It will be shown that the application to SubPcs of the design criteria that have been successful in phthalocyanines and porphyrins led to high-performance second-harmonic generators
Conjugated copolymer derivatives of poly[2-methoxy-5-(3&a... more Conjugated copolymer derivatives of poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) and poly(3-hexylthiophene) (P3HT) containing 10% of alkyne functionalities in the side chains have been prepared using the sulfinyl precursor route and the Rieke method, respectively. With the aim of expanding the absorption range of these conjugated polymers for their use in bulk heterojunction (BHJ) polymer:fullerene solar cells, appropriate phthalocyanine (Pc) molecules have been covalently bound through a post-polymerization "click chemistry" reaction between the alkyne functionalities in the side chains of the copolymers and a Pc functionalized with an azide moiety. The resulting poly(p-phenylenevinylene)-Pc (PPV-Pc) material holds a 9 mol% content of Pcs, while the polythiophene-Pc material (PT-Pc) contains a 8 mol% of Pc-functionalization in the side chains. As expected, the presence of the Pc contributes to the extension of the absorption up to 700 nm. BHJ solar cells have been prepared using PPV-Pc and PT-Pc materials in combination with PCBM. Although the Pc absorption contributes to the generation of photocurrent, the overall power conversion efficiencies (PCE) obtained from these cells are lower than those obtained with BHJ P3HT:PCBM (1:1) and MDMO-PPV:PCBM (1:4) solar cells. A plausible explanation could be the moderate solubility of the PPV-Pc and PT-Pc materials that limits the processing into thin films.
Two triads (donor–spacer–acceptor), exTTF–BN–C60 (6) and ZnP–BN–C60 (7), in which electron donors... more Two triads (donor–spacer–acceptor), exTTF–BN–C60 (6) and ZnP–BN–C60 (7), in which electron donors (i.e., exTTF or ZnP) are covalently linked to C60 through a chiral binaphthyl bridge (BN), have been prepared in a multistep synthetic procedure starting from a highly soluble enantiomerically pure binaphthyl building block (1). Unlike other oligomeric bridges, with binaphthyl bridges, the conjugation between the donor and the acceptor units is broken and geometric conformational changes are facilitated. Consequently, distances and electronic interactions between the donor and C60 are drastically changed. Both donor–spacer–acceptor (D–s–A) systems (i.e., 6 and 7) exhibit redox processes that correspond to all three constituent electroactive units, namely, donor, BN, and C60. Appreciable differences were, however, observed when comparing triad 6, in which no significant exTTF–C60 interactions were noted, with D–s–A 7, whose geometry favors donor–acceptor and π–π interactions that result ...
A series of homoleptic ([TbIII(Pc)2]) and heteroleptic ([TbIII(Pc)(Pc′)]) TbIII bis(phthalocyanin... more A series of homoleptic ([TbIII(Pc)2]) and heteroleptic ([TbIII(Pc)(Pc′)]) TbIII bis(phthalocyaninate) complexes that contain different peripheral substitution patterns (i.e., tert‐butyl or tert‐butylphenoxy groups) have been synthesized in their neutral radical forms and then reduced into their corresponding anionic forms as stable tetramethylammonium/tetrabutylammonium salts. All of these compounds were spectroscopically characterized and their magnetic susceptibility properties were investigated. As a general trend, the radical forms exhibited larger energy barriers for spin reversal than their corresponding reduced compounds. Remarkably, heteroleptic complexes that contain electron‐donor moieties on one of the two Pc ligands show higher effective barriers and blocking temperatures than their homoleptic derivatives. This result is assigned to the elongation of the NTb distances in the substituted macrocycle, which brings the terbium(III) ion closer to the unsubstituted Pc, thus e...
A photoredox cage built by coordination of two pyridyl-subphthalocyanines to Pd centers has prove... more A photoredox cage built by coordination of two pyridyl-subphthalocyanines to Pd centers has proved versatile and efficient to catalyze photoredox addition reactions over encapsulated C60.
Photodynamic therapy combines light, molecular oxygen and a PS for the production of reactive oxy... more Photodynamic therapy combines light, molecular oxygen and a PS for the production of reactive oxygen species (ROS), such as singlet oxygen (1O2) and free radicals, leading to oxidative stress and eventual cell death. Phthalocyanines (Pcs) fulfil many of the requirements to be applied as photosensitizers for singlet oxygen generation.1,2 However, a major drawback of these compounds is their low solubility in physiological media. Functionalization of the macrocycle at the peripheral and/or axial positions with appropriate hydrophilic functions provides compounds with an enhanced solubility in water. In this respect, several strategies have been adopted to increase the hydrophilicity of Pcs and make them more bio-compatible, like their functionalization with charged groups,3 aminoacids4 or carbohydrates.5 The introduction of such entities at Pc axial positions reduces the aggregation of the macrocycles in solution, thus improving their 1O2 generation efficiency. For recent work of our ...
In this manuscript, we have studied the selectivity in the complexation of fullerene species by a... more In this manuscript, we have studied the selectivity in the complexation of fullerene species by a Fe[Formula: see text]Pc[Formula: see text] metallo-organic helicate (1) assembled using a bidentate phthalocyanine (Pc) as ligand. The large aromatic internal surface of this helicate shows a strong selectivity towards the encapsulation of C[Formula: see text] from a mixture of C[Formula: see text] and C[Formula: see text]. On the other hand, a bisimidazole-containing naphthalenediimide was used to perform guest exchange experiments over [fullerene [Formula: see text] 1] complexes, taking advantage of the strong coordination bond of the imidazole ring to the Zn centers in the Pc cavity.
Stable macrocyclic compounds based on phthalocyanines and porphyrins as hole- and electron-transp... more Stable macrocyclic compounds based on phthalocyanines and porphyrins as hole- and electron-transporting materials for perovskite solar cells are reviewed.
Chemistry (Weinheim an der Bergstrasse, Germany), Jan 13, 2018
Two zinc phthalocyanines (ZnPcs) have been equipped with Newkome-type dendritic branches of incre... more Two zinc phthalocyanines (ZnPcs) have been equipped with Newkome-type dendritic branches of increasing size and number of terminal carboxylate functional groups. The negatively charged carboxylates render these polyelectrolytes soluble in polar media such as methanol or buffered water. Sonication of the ZnPcs with graphene allowed for pronounced non-covalent binding of the Pc moieties on the graphene surface. These hybrid systems were fully characterized via UV/vis, AFM, TEM, Raman and transient absorption spectroscopy, yielding insights into the electron donating nature of the novel phthalocyanine structures.
Challenges and Advances in Computational Chemistry and Physics, 2006
ABSTRACT Boron-subphthalocyanines (SubPcs)—cone-shaped 14-π electron aromatic macrocycles—are low... more ABSTRACT Boron-subphthalocyanines (SubPcs)—cone-shaped 14-π electron aromatic macrocycles—are lower phthalocyanine analogues which consist of three isoindole units N-fused around a central boron atom which fourth valency is occupied by an axial ligand. SubPcs have been shown to possess very interesting features for NLO. Although they present a permanent dipole moment along the boron-axial substituent axis, their optical response is essentially associated to charge transfer inside the macrocycle π-surface. Moreover, due to the C3v symmetry of the SubPc core, its NLO behavior is mostly octupolar. It will be shown that the application to SubPcs of the design criteria that have been successful in phthalocyanines and porphyrins led to high-performance second-harmonic generators
Conjugated copolymer derivatives of poly[2-methoxy-5-(3&a... more Conjugated copolymer derivatives of poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) and poly(3-hexylthiophene) (P3HT) containing 10% of alkyne functionalities in the side chains have been prepared using the sulfinyl precursor route and the Rieke method, respectively. With the aim of expanding the absorption range of these conjugated polymers for their use in bulk heterojunction (BHJ) polymer:fullerene solar cells, appropriate phthalocyanine (Pc) molecules have been covalently bound through a post-polymerization "click chemistry" reaction between the alkyne functionalities in the side chains of the copolymers and a Pc functionalized with an azide moiety. The resulting poly(p-phenylenevinylene)-Pc (PPV-Pc) material holds a 9 mol% content of Pcs, while the polythiophene-Pc material (PT-Pc) contains a 8 mol% of Pc-functionalization in the side chains. As expected, the presence of the Pc contributes to the extension of the absorption up to 700 nm. BHJ solar cells have been prepared using PPV-Pc and PT-Pc materials in combination with PCBM. Although the Pc absorption contributes to the generation of photocurrent, the overall power conversion efficiencies (PCE) obtained from these cells are lower than those obtained with BHJ P3HT:PCBM (1:1) and MDMO-PPV:PCBM (1:4) solar cells. A plausible explanation could be the moderate solubility of the PPV-Pc and PT-Pc materials that limits the processing into thin films.
Two triads (donor–spacer–acceptor), exTTF–BN–C60 (6) and ZnP–BN–C60 (7), in which electron donors... more Two triads (donor–spacer–acceptor), exTTF–BN–C60 (6) and ZnP–BN–C60 (7), in which electron donors (i.e., exTTF or ZnP) are covalently linked to C60 through a chiral binaphthyl bridge (BN), have been prepared in a multistep synthetic procedure starting from a highly soluble enantiomerically pure binaphthyl building block (1). Unlike other oligomeric bridges, with binaphthyl bridges, the conjugation between the donor and the acceptor units is broken and geometric conformational changes are facilitated. Consequently, distances and electronic interactions between the donor and C60 are drastically changed. Both donor–spacer–acceptor (D–s–A) systems (i.e., 6 and 7) exhibit redox processes that correspond to all three constituent electroactive units, namely, donor, BN, and C60. Appreciable differences were, however, observed when comparing triad 6, in which no significant exTTF–C60 interactions were noted, with D–s–A 7, whose geometry favors donor–acceptor and π–π interactions that result ...
A series of homoleptic ([TbIII(Pc)2]) and heteroleptic ([TbIII(Pc)(Pc′)]) TbIII bis(phthalocyanin... more A series of homoleptic ([TbIII(Pc)2]) and heteroleptic ([TbIII(Pc)(Pc′)]) TbIII bis(phthalocyaninate) complexes that contain different peripheral substitution patterns (i.e., tert‐butyl or tert‐butylphenoxy groups) have been synthesized in their neutral radical forms and then reduced into their corresponding anionic forms as stable tetramethylammonium/tetrabutylammonium salts. All of these compounds were spectroscopically characterized and their magnetic susceptibility properties were investigated. As a general trend, the radical forms exhibited larger energy barriers for spin reversal than their corresponding reduced compounds. Remarkably, heteroleptic complexes that contain electron‐donor moieties on one of the two Pc ligands show higher effective barriers and blocking temperatures than their homoleptic derivatives. This result is assigned to the elongation of the NTb distances in the substituted macrocycle, which brings the terbium(III) ion closer to the unsubstituted Pc, thus e...
A photoredox cage built by coordination of two pyridyl-subphthalocyanines to Pd centers has prove... more A photoredox cage built by coordination of two pyridyl-subphthalocyanines to Pd centers has proved versatile and efficient to catalyze photoredox addition reactions over encapsulated C60.
Photodynamic therapy combines light, molecular oxygen and a PS for the production of reactive oxy... more Photodynamic therapy combines light, molecular oxygen and a PS for the production of reactive oxygen species (ROS), such as singlet oxygen (1O2) and free radicals, leading to oxidative stress and eventual cell death. Phthalocyanines (Pcs) fulfil many of the requirements to be applied as photosensitizers for singlet oxygen generation.1,2 However, a major drawback of these compounds is their low solubility in physiological media. Functionalization of the macrocycle at the peripheral and/or axial positions with appropriate hydrophilic functions provides compounds with an enhanced solubility in water. In this respect, several strategies have been adopted to increase the hydrophilicity of Pcs and make them more bio-compatible, like their functionalization with charged groups,3 aminoacids4 or carbohydrates.5 The introduction of such entities at Pc axial positions reduces the aggregation of the macrocycles in solution, thus improving their 1O2 generation efficiency. For recent work of our ...
In this manuscript, we have studied the selectivity in the complexation of fullerene species by a... more In this manuscript, we have studied the selectivity in the complexation of fullerene species by a Fe[Formula: see text]Pc[Formula: see text] metallo-organic helicate (1) assembled using a bidentate phthalocyanine (Pc) as ligand. The large aromatic internal surface of this helicate shows a strong selectivity towards the encapsulation of C[Formula: see text] from a mixture of C[Formula: see text] and C[Formula: see text]. On the other hand, a bisimidazole-containing naphthalenediimide was used to perform guest exchange experiments over [fullerene [Formula: see text] 1] complexes, taking advantage of the strong coordination bond of the imidazole ring to the Zn centers in the Pc cavity.
Stable macrocyclic compounds based on phthalocyanines and porphyrins as hole- and electron-transp... more Stable macrocyclic compounds based on phthalocyanines and porphyrins as hole- and electron-transporting materials for perovskite solar cells are reviewed.
Chemistry (Weinheim an der Bergstrasse, Germany), Jan 13, 2018
Two zinc phthalocyanines (ZnPcs) have been equipped with Newkome-type dendritic branches of incre... more Two zinc phthalocyanines (ZnPcs) have been equipped with Newkome-type dendritic branches of increasing size and number of terminal carboxylate functional groups. The negatively charged carboxylates render these polyelectrolytes soluble in polar media such as methanol or buffered water. Sonication of the ZnPcs with graphene allowed for pronounced non-covalent binding of the Pc moieties on the graphene surface. These hybrid systems were fully characterized via UV/vis, AFM, TEM, Raman and transient absorption spectroscopy, yielding insights into the electron donating nature of the novel phthalocyanine structures.
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