Porphyrazine Binaries:  Synthesis, Characterization, and Spectroscopy of a Metal-Linked Trinuclear Porphyrazine Dimer

Baumann, Theodore F.; Barrett, Anthony G. M.; Hoffman, Brian M.

doi:10.1021/ic9701367

Cited by 70 publications

(86 citation statements)

References 36 publications

(40 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…UV/Vis spectroscopy: Shimadzu UV-365. 1 (1), [2] bis(4-tert-butylphenyl)fumaronitrile (A), [15] 5,6-dicyano-1H-benzotriazole (B), [9] and 1-aminobenzotriazole (15) [6] were prepared as described earlier. Other chemicals and solvents were purchased from commercial sources and were used without additional purification, unless mentioned.…”

Section: Methodsmentioning

confidence: 99%

Reactivity of Dehydrometallophthalocyanines and ‐porphyrazines

Vagin

Frickenschmidt

Kammerer

et al. 2007

Chemistry A European J

View full text Add to dashboard Cite

The zinc dehydrophthalocyanine 2 and zinc dehydrobenzoporhyrazine 8 a were generated from the 1N-aminobenzotriazole-annulated zinc phtalocyanine 1 and zinc benzoporhyrazine 8, respectively, by oxidation with Pb(OAc)(4) in different solvents, for example, diethyl ether, tetrahydrofuran, acetic acid, and benzene. The reactivity of 2 and 8 a was studied in detail. These species not only easily undergo Diels-Alder additions with dienes, but also the used solvents can be added. Among the addition products with solvents ethoxy-, acetoxy-, acetoxybutyloxy-substituted and barrelen-fused phthalocyanines and benzoporpyrazines were isolated. No products resulting from the dimerization of two dehydro species were observed either for 2 or 8 a. Analysis of the reaction products in comparison with those obtained by oxidation of 1-aminobenzotriazole 15 under similar conditions proves a higher reactivity (electrophilicity) of the dehydro-PcZn 2 and dehydro-PzZn 8 a in comparison with unsubstituted benzyne towards the solvents used, such as diethyl ether and benzene.

show abstract

Section: Methodsmentioning

confidence: 99%

Reactivity of Dehydrometallophthalocyanines and ‐porphyrazines

Vagin

Frickenschmidt

Kammerer

et al. 2007

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…[268][269][270][271][272][273][274][275] For instance, asymmetric A 3 B type phthalocyanine analogues can easily form mono-or dinuclear phthalocyanine analogues 92-95 when reacted with the main-group or transition-metal ions ( Figure 6). Similarly, Ercolani and co-workers have shown that six out of eight available pyridine-type nitrogen atoms in symmetric phthalocyanine could be methylated using standard methylation agents.…”

Section: Peripheral Substituent Coordination Approachmentioning

confidence: 99%

Synthetic approaches to asymmetric phthalocyanines and their analogues

Nemykin¹,

Dudkin²,

Dumoulin³

et al. 2014

Arkivoc

View full text Add to dashboard Cite

This review summarizes synthetic strategies for the preparation of asymmetric phthalocyanines and their analogues. Cross-condensation between two phthalonitrile components, crosscondensation between one phthalonitrile and one non-nitrile component, targeted synthesis of AABB-type compounds, the subphthalocyanine ring-expansion method, as well as postmodification approaches on pre-formed symmetric and asymmetric systems, are discussed. Methodologies for targeted preparation of specific types of asymmetric phthalocyanines and their analogues are also briefly overviewed.

show abstract

“…56b), which is of LLCT nature. Our calculations for the monomer 1 with -tBu substituents compared with calculations performed on the octamethyl substituted [TiO-Pz] [20] indeed show that the -tBu substituents have effect over the Q band energy (Table III) has also investigated the influence of the alkyl substitution in porphyrins, stating that the substitutions may produce excitation energies downward shifts of as much as 0.2-0.3 eV. From the other side, ligand to metal charge transfer (LMCT) transitions are also expected to play a role in complexes 2-7 because of the presence of d xy orbitals into the valence region.…”

Section: Tddft Analysis: Absorption Spectramentioning

confidence: 99%

“…But owing to efficient synthetic routes reported by Fitzgerald et al [16] and Rodríguez-Morgade and Stuzhin [17], it has increased the study of their properties and applications [18][19][20][21][22][23]. Pz is constituted by four tetrapyrroles and nitrogens in position meso, and also they are called tetra-azaporphyrins.…”

Section: Introductionmentioning

confidence: 99%

“…Pz is constituted by four tetrapyrroles and nitrogens in position meso, and also they are called tetra-azaporphyrins. Experimental and theoretical studies show a variety of tetra-azaporphyrin complexes with metallic center like Ti, Ni, Zn, and rareearths, forming diverse types of dimers, trimers, and oligomers [18][19][20]. Similarly, density functional theory (DFT) and time dependent DFT (TDDFT) methodologies have been used by Muñ oz-Castro et al [24] to study the electronic structure of Cd(II) multidecker phthalocyanine compounds, where the authors take into account the spin-orbit interaction.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

A DFT/TDDFT study of porphyrazines and phthalocyanine oxo‐titanium derivatives as potential dyes in solar cells

Zarate

Schott

Arratia‐Pérez

2011

Int J of Quantum Chemistry

View full text Add to dashboard Cite

Density functional theory and time dependent density functional theory calculations at the level of LDA/BP86/TZ2P were performed systematically on several Ti(IV) complexes of porphyrazines and one phthalocyanine. We performed an analysis of the frontier molecular orbitals of the ground state electronic structures and also discuss in particular the good concordance of our results with the experimental data, which affords to predict the geometrical and optical properties of new complexes (3, 4, and 7). We also emphasize the characterization of the UV-vis absorption spectra and propose transitions that contribute to the Q and B bands. Some useful calculated properties in complexes 2, 3, and 7, like: high light absorption in the visible region of the spectra, transitions involved in these bands with a determined direction, charge separation, bigger highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gaps than complexes 4 and 5, and the energy of their LUMO orbitals (that are higher than the lowest energy level of the conduction band of the TiO 2 ) indicate that system complexes 2, 3, and 7 could act as light-harvesting sensitizers for dye-sensitized solar cells (DSCs). These proposals were made using a model of the previously experimentally known phthalocyanine, which was used as sensitizer in DSCs devices, comparing its electronic properties with the herein proposed sensitizers.

show abstract

Porphyrazine Binaries: Synthesis, Characterization, and Spectroscopy of a Metal-Linked Trinuclear Porphyrazine Dimer

Cited by 70 publications

References 36 publications

Reactivity of Dehydrometallophthalocyanines and ‐porphyrazines

Reactivity of Dehydrometallophthalocyanines and ‐porphyrazines

Synthetic approaches to asymmetric phthalocyanines and their analogues

A DFT/TDDFT study of porphyrazines and phthalocyanine oxo‐titanium derivatives as potential dyes in solar cells

Contact Info

Product

Resources

About