Solvent-Free Synthesis of Soluble, Near-IR Absorbing Titanyl Phthalocyanine Derivatives

Mayukh, Mayank; Sema, Clarissa M.; Roberts, Jessica M.; McGrath, Dominic V.

doi:10.1021/jo1011637

Cited by 16 publications

(20 citation statements)

References 41 publications

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“…13,15,19,21,96 Though designed porphyrins and phthalocyanines that are made in low synthetic yields can have better performance, we focus on commercial viable dye systems that can be made in good yields using green chemistry and click-type reactions to append exocyclic motifs. 97,98 Addition of cooadsorbants to the system, which are reported to suppress aggregation of porphyrinoid dyes and to reduce back electron transfer, 87,99 may improve the performance as well.…”

Section: Discussionmentioning

confidence: 99%

Zirconium(IV) and Hafnium(IV) Porphyrin and Phthalocyanine Complexes as New Dyes for Solar Cell Devices

et al. 2012

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Metalloporphyrin and metallophthalocyanine dyes ligating Hf(IV) and Zr(IV) ions bind to semiconductor oxide surfaces such as TiO2 via the protruding group IV metal ions. The use of oxophylic metal ions with large ionic radii that protrude from the macrocycle is a unique mode of attaching chromophores to oxide surfaces in the design of dye-sensitized solar cells (DSSCs). Our previous report on the structure and physical properties of ternary complexes wherein the Hf(IV) and Zr(IV) ions are ligated to both a porphyrinoid and to a defect site on a polyoxometalate (POM) represents a model for this new way of binding dyes to oxide surfaces. The Zr(IV) and Hf(IV) complexes of 5,10,15,20-tetraphenylporphyrin (TPP) with two ligated acetates, (TPP)Hf(OAc)2 and (TPP)Zr(OAc)2, and the corresponding metallophthalocyanine (Pc) diacetate complexes, (Pc)Hf(OAc)2 and (Pc)Zr(OAc)2, were evaluated as novel dyes for the fabrication of dye-sensitized solar cells. Similarly to the ternary complexes with the POM, the oxide surface replaces the acetates to affect binding. In DSSCs the Zr(IV) phthalocyanine dye performs better than the Zr(IV) porphyrin dye, and reaches an overall efficiency of ~ 1.0%. The Hf(IV) dyes are less efficient. The photophysical properties of these complexes in solution suggested energetically favorable injection of electrons into the conduction band of TiO2 semiconductor nanoparticles, as well as a good band gap match with I3−/I− pair in liquid 1-butyl-3-methyl imidazolium iodide. The combination of blue absorbing TPP with the red absorbing Pc complexes can increase the absorbance of solar light in the device; however, the overall conversion efficiency of DSSCs using TiO2 nanoparticles treated with a mixture of both Zr(IV) complexes is comparable, but not greater than, the single (Pc)Zr. Thus, surface bound (TPP)Zr increases the absorbance in blue region of the spectra, but at the cost of diminished absorbance in the red in this DSSC architecture.

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Section: Discussionmentioning

confidence: 99%

Zirconium(IV) and Hafnium(IV) Porphyrin and Phthalocyanine Complexes as New Dyes for Solar Cell Devices

et al. 2012

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“…To this end, samples were prepared according to the procedures reported in literature. [9,[20][21] In general, for ligands 2a-c, the precursor ion results from the addition of a proton to form the positively…”

Section: Maldi-tof Analysismentioning

confidence: 99%

“…[4][5][6] In general, in oxidizing atmosphere, titanium exists as Ti(IV) and it can be coordinated by tetrapyrrole ligands as a titanyl unit (TiO 2+ ). [7][8][9][10] In this paper, we present the synthesis and the characterization of a series of ligands and Ti-based complexes of tetrakis-2,3-[5,6-di-R 8 -pyrazino]porphyrazine (R = H, 2-Py, Ph). For all the compounds (2a-c and 3a-c, Scheme 1) a full spectroscopic and electrochemical characterization is presented.…”

Section: Introductionmentioning

confidence: 99%

Titanium‐Based Tetrakis‐2,3‐[5,6‐di(Substituted)pyrazino]porphyrazine: Synthesis and Characterization

et al. 2020

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Tetrapyrazinoporphyrazine (TPysPz) ligands and metal complexes find, generally, application as electronic materials and catalysts. Considering the limited application of Titanium (Ti), we prepared and characterized a family of ligands and Ti-based complexes of tetrakis-2,3-[5,6-di-R 8-pyrazino]porphyrazine (R = H, 2-Py, Ph). UV/Vis measurements in different solvents confirm molecular aggregation, which results more pronounced in the presence of 2-pyridil and phenyl substituents on the macrocycle edge. Because of low solubility, solid state NMR was applied for structure characterization.

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“…2,[23][24][25] Until now several substituted titanyl and vanadyl phthalocyanines were obtained. [26][27][28] However, the molecular structure was determined for unsubstituted titanyl and vanadyl phthalocyanines only using the Rietveld method on powdered samples 29,30 or crystals, 31 respectively.…”

Section: Introductionmentioning

confidence: 99%

Radical anion and dianion salts of titanyl macrocycles with acceptor substituents or an extended π-system

et al. 2017

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Crystalline anionic salts of titanyl macrocycles with acceptor substituents or an extended π-system have been obtained for the first time: (PPN){O[double bond, length as m-dash]Ti(PcCl)} (1), (PPN){O[double bond, length as m-dash]Ti(Nc˙)}˙·2CHCl (2) and (PPN){O[double bond, length as m-dash]Ti(AceTPrzPz)}·1.3CHCl·0.8CHCN (3) where PPN is the bis(triphenylphosphoranylidene)ammonium cation, PcCl - 2,3,9,10,16,17,23,24-octachlorophthalocyanine; Nc - 2,3-naphthalocyanine, AceTPrzPz - tetra(acenaphthenopyrazino)porphyrazine. Salts 1-3 were obtained in the reduction of the parent titanyl macrocycles by fluorenone ketyl in the presence of an excess of PPNCl in o-dichlorobenzene with following precipitation of crystals with n-hexane. Reduction of macrocycles in 1-3 is accompanied by the appearance of intense NIR bands in the solid spectra at 963-1159 nm. It has been found that the extended π-system with linear annulation in {O[double bond, length as m-dash]Ti(Nc˙)}˙ provides the shift of the NIR band to smaller energies (1159 nm) in comparison with those in the spectra of {O[double bond, length as m-dash]Ti(Pc˙)}˙ (995-998 nm). Reduction of macrocycles leads also to the alternation of C-N bonds due to partial disruption of their aromaticity. The disruption is higher for the dianions in 1 and 3 in comparison with the radical anions in 2. One-dimensional π-π stacking chains and layers are formed in 1 and 3 with diamagnetic {O[double bond, length as m-dash]Ti(PcCl)} and {O[double bond, length as m-dash]Ti(AceTPrzPz)} dianions, respectively. Salt 2 contains nearly isolated [{O[double bond, length as m-dash]Ti(Nc˙)}˙] dimers with a strong π-π interaction between paramagnetic radical anion macrocycles. As a result, a transition from the triplet to singlet state with antiparallel ordering of spins within the dimers is observed in 2 below 200 K.

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Solvent-Free Synthesis of Soluble, Near-IR Absorbing Titanyl Phthalocyanine Derivatives

Cited by 16 publications

References 41 publications

Zirconium(IV) and Hafnium(IV) Porphyrin and Phthalocyanine Complexes as New Dyes for Solar Cell Devices

Zirconium(IV) and Hafnium(IV) Porphyrin and Phthalocyanine Complexes as New Dyes for Solar Cell Devices

Titanium‐Based Tetrakis‐2,3‐[5,6‐di(Substituted)pyrazino]porphyrazine: Synthesis and Characterization

Radical anion and dianion salts of titanyl macrocycles with acceptor substituents or an extended π-system

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