- Synthesis, structural and conformational analysis and chemical properties of phthalocyaninatometal complexes
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Syntheses of the phthalocyaninatometal complexes were performed and the crystal and molecular structures were determined by single-crystal X-ray diffraction analysis. The general formulas of these Pc dye compounds are -[Si(Pc)OSiR2/1R2SiR2/1O](n)-and Si(Pc)(OSiR1R2R3)2: -[Si(Pc)OSi(CH3)2(CH2)7Si(CH3)2O](n)- (1), Si(Pc)[OSi(C6H13)3]2 (2) Si(Pc)[OSiC8H17(CH3)2]2 (3) and Si(Pc)[OSiCH3C12H25CH3]2 (4). These Pc dye derivatives were prepared by refluxing a mixture of Si(Pc)(OH)2 and SiR1R2R3Cl in pyridine, followed by cooling the mixture slowly and then drying the resulting precipitates. For 1-3, the Pc skeleton and the oxo-bridged substituentes are coplanar. The dihedral angle between the mean planes of the Pc skeleton and two single-atom Si(me) [Si(me)-O-Si(pc)-O-Si(me)] is nearly at right angles. The Si(pc)-O bonds are shorter than the Si(pc)-N bonds and the Si(me)-O bonds are shorter than the Si(pc)-O bonds. For 1, the Pc microcyclic rings are related by a center of symmetry at the center of the O1-Si1-O2 bonds. The chemical formula of a mononer is C43H42N8O2Si3 (C25H28N5O2Si3 in crystallographic symmetry) and the polymer is built up by the addition polymerization of the monomers. The polymer chain is constructed at the siloxy group along the a axis. Two hexyl groups of two siloxy side groups for 2 have the same direction, but one hexyl extends in the opposite direction. For 3, two methyl groups and one octyl group extend in the opposite direction. We applied Pc dyes 2-4, mixed with a polymer for the control of the aggregation state to CD-R and DVD-R recording systems. The aggregation state of the recording layer is controlled by choosing the set of axial substituents R1-R3. The interactions of Pc dyes with polymers are dependant upon the length of axial substituents. We achieved the best writing contrast and the highest stability with the mixed PC dye 4. The conformation of axial substituents is very important for the ability of the dye aggregation and the capability to control the aggregation state.
- Sasa, Noboru,Okada, Kenji,Nakamura, Kazuo,Okada, Sachiko
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- Silicon Phthalocyanines Axially Disubstituted with Erlotinib toward Small-Molecular-Target-Based Photodynamic Therapy
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Small-molecular-target-based photodynamic therapy—a promising targeted anticancer strategy—was developed by conjugating zinc(II) phthalocyanine with a small-molecular-target-based anticancer drug. To prevent self-aggregation and avoid problems of phthalocyanine isomerization, two silicon phthalocyanines di-substituted axially with erlotinib have been synthesized and fully characterized. These conjugates are present in monomeric form in various solvents as well as culture media. Cell-based experiments showed that these conjugates localize in lysosomes and mitochondria, while maintaining high photodynamic activities (IC50 values as low as 8 nm under a light dose of 1.5 J cm?2). With erlotinib as the targeting moiety, two conjugates were found to exhibit high specificity for EGFR-overexpressing cancer cells. Various poly(ethylene glycol) (PEG) linker lengths were shown to have an effect on the photophysical/photochemical properties and on in vitro phototoxicity.
- Chen, Juan-Juan,Huang, Yi-Zhen,Song, Mei-Ru,Zhang, Zhi-Hong,Xue, Jin-Ping
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- Photoactive Surface-Grafted Polymer Brushes with Phthalocyanine Bridging Groups as an Advanced Architecture for Light-Harvesting
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Surface-grafted polymer brushes of novel ladder-like architecture were proposed for inducing ordering of chromophores embedded therein. The brushes with acetylene side groups were obtained by surface-initiated photoiniferter-mediated polymerization. The acetylene moieties reacted then through a “click” process with an axially azide-bifunctionalized silicon phthalocyanine bridging the neighboring chains that inherently adopt extended conformations in dense brushes. FTIR, quartz crystal microbalance, and atomic force microscopy were used to study formation and structure of the photoactive brushes varying in grafting densities. Importantly, photophysical properties of the chromophores were virtually unaffected upon embedding them into the brushes, as evidenced by UV/Vis absorption and emission spectroscopy. Owing to the unique ordering of the chromophores, the proposed method may open new opportunities for the fabrication of light-harvesting systems suitable for photovoltaic or sensing applications.
- Szuwarzyński, Micha?,Wolski, Karol,Pomorska, Agata,Uchacz, Tomasz,Gut, Arkadiusz,?apok, ?ukasz,Zapotoczny, Szczepan
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- Synthesis and characterization of phthalocyaninatosilicon with bridging ligands (L) (L = Dimethylsilane, diphenylsilane, methylphenylsilane)
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Several new types of cofacial compounds of μ-(dimethylsilane)phthalocyaninatosilicon [PcSi(dms)]n, μ-(diphenyl-silane)phthalocyaninatosilicon [PcSi(dps)]n, and μ-(methylphenylsilane)phthalocyaninatosilicon [PcSi(mps)]n were synthesized by the reaction of dichlorophthalocyaninatosilicon (PcSiCl2) with dichlorodimethylsilane, dichlorodiphenylsilane, and dichloromethylphenylsilane in xylene, respectively. The corresponding silane-bridged phthalocyaninatosilicon compounds were characterized by Fourier transform infrared (FT-IR), 29Si-NMR, UV-vis, elemental analysis, and thermogravimetry/differential thermal analysis (TG/DTA). The electrical conductivities of the compounds were measured by the four-probe method, and the bridged phthalocyaninatosilicon compounds without the dopant showed very low electrical conductivity. A clear increase in conductivity, however, was observed for the doped compounds [PcSi(L)Iy]n and [PcSi(L) (ClO4)y]n, which was found to be in the range σRT = 10-6-10-3 S/cm with doping (I2, AgClO4).
- Park, Ha Sun,Ryu, Haiil,Jang, Nak Han
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- Bis(tri-n-alkylsilyl oxide) silicon phthalocyanines: A start to establishing a structure property relationship as both ternary additives and non-fullerene electron acceptors in bulk heterojunction organic photovoltaic devices
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Previous studies have shown that the use of bis(tri-n-hexylsilyl oxide) silicon phthalocyanine ((3HS)2-SiPc) as a solid ternary electroactive additive in poly(3-hexylthiophene):phenyl-C61-butyric acid methyl ester P3HT:PC61BM bulk heterojunction organic photovoltaic (BHJ OPV) devices resulted in an increased performance. It has been hypothesized that the increase in efficiency is partially due to the unique and odd combination of high solubility and strong driving force of crystallization previously observed for (3HS)2-SiPc. In this follow-up study, two chemical variants of (3HS)2-SiPc, namely bis(tri-n-butylsilyl oxide) ((3BS)2-SiPc) and bis(tri-n-isopropylsilyl oxide) ((3TS)2-SiPc) were synthesized to determine how small changes in the chemical structure would affect the properties of the material and its performance within BHJ OPV devices. We observed that the use of either (3XS)2-SiPc compound results in a further ～10% increase in JSC compared to the use of (3HS)2-SiPc. We also did a preliminary assessment of the use of three (3XS)2-SiPcs as replacements for PC61BM in straight binary P3HT-based BHJ OPV devices. Despite achieving only ～1% PCE efficiencies, observations including a ≈50% increase in VOC over a P3HT:PC61BM baseline and a decent fill factor indicate to us that (3XS)2-SiPcs do have potential as non-fullerene acceptors and advantageous alternatives due to their low embedded energy and therefore their inherent sustainability. X-ray diffraction of ternary and binary BHJ devices demonstrates that both (3BS)2-SiPc and (3TS)2-SiPc experienced similar increase in crystallite density (d-spacing) relative to (3HS)2-SiPc which we surmise plays a role in the improved device efficiency. Like (3HS)2-SiPc, for these two new additives, we also observed a high tendency of crystallization. The results from this study suggest that solubility and driving force to crystallize are important factors in determining the extent to which an additive will migrate to the donor/acceptor interface and thus affect its performance as a ternary additive in BHJ OPV devices. Based on the three (3XS)2-SiPcs used in this study, the smaller tri-n-alkylsilyl oxide molecular fragments seem to work better. Therefore, moving forward, we will continue to consider smaller molecular fragments that still enable solubility and processability of (3XS)2-SiPcs.
- Dang, Minh-Trung,Grant, Trevor M.,Yan, Han,Seferos, Dwight S.,Lessard, Beno?t H.,Bender, Timothy P.
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- Ab-initio X-ray powder structure analysis of two polymorphs of dihydroxysilicon phthalocyanine
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This paper reports on the synthesis and ab-initio X-ray powder structure determination of two polymorphs of [Si(OH)2Pc], where Pc = phtalocyaninato. We found that one of the polymorphs (Phase II) shows high sensitivity for an electrophotographic photoreceptor, but that the other (Phase I) doesn't have photosensitivity. The difference in the sensitivity depends on only the crystal structures. This material has not been able to be grown to a single crystal with sufficient size for single crystal X-ray analysis, but it is very important to determine the crystal structures of the two polymorphs for understanding the mechanism of the performance of the electrophotographic photoreceptor. In this work we carried out ab-initio X-ray powder structure analysis. The compound crystallizes in space group P1 (Phase I), Z = 1 with unit-cell parameters of a = 12.992(1), b = 7.2830(8), c = 6.861(1) A, α = 104.413(7)°, β = 101.757(8)°, γ = 96.973(6)°and in space group P21/n (Phase II), Z = 2 with unit-cell parameters of a = 12.7494(5), b = 14.5778(6), c = 6.7727(3) A, β = 94.353(2)°. Both phases have symmetry center in the molecules (on Si atom) and intermolecular hydrogen bonds (O-H ··· N). These hydrogen bond modes of Phase I and Phase II are the same. The main difference in packings was revealed between the crystals: Phase II crystal has the herringbone structure, while in Phase I all molecules form the parallel stack columns.
- Kojima, Yuko,Osano, Yasuko T.,Ohashi, Toyoshi
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- Preparation method of di-(4-dibenzothiophene-2-phenoxy) axially substituted silicon phthalocyanine
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The invention belongs to a preparation method of a di-(4-dibenzothiophene-2-phenoxy) axially substituted silicon phthalocyanine complex. The complex is used as a photosensitizer for antibacterial treatment. The preparation method comprises the following steps: (1) adding 2-bromodibenzothiophene, 4-hydroxyphenylboronic acid, 1, 3-dibromopropane and tetrakis(triphenylphosphine) palladium into a mixed solution of tetrahydrofuran and anhydrous K2CO3, stirring and mixing, and refluxing to prepare a precursor 4-dibenzothiophene-2-phenol, and (2) adding the precursor 4-dibenzothiophene-2-phenol and dichlorosilane (IV) phthalocyanine into a toluene solution in the presence of anhydrous K2CO3, stirring and mixing at 140 DEG C, and refluxing to prepare the di-(4-dibenzothiophene-2-phenoxy) substituted silicon phthalocyanine. According to the silicon phthalocyanine prepared by the invention, the steric hindrance of an aryl thiophene structure is utilized to inhibit the formation of phthalocyanineaggregate, and benzothiophene is introduced to the axial position of phthalocyanine, so that the silicon phthalocyanine has antimicrobial and anticancer effects and can be applied to photosensitizers.
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Paragraph 0029-0032
(2021/03/11)
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- Water-soluble mitochondrial targeting ethoxy-bromopropyl imidazole axial substituted silicon phthalocyanine and preparation method and application thereof
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The invention discloses a water-soluble mitochondrial targeting ethoxy-bromopropyl imidazole axial substituted silicon phthalocyanine and a preparation method and application thereof. The invention relates to a water-soluble mitochondrial targeting di - (1 - (2 - ethoxy) -3 - (3 - bromopropyl) imidazole) axial substituted silicon phthalocyanine and a preparation method and application thereof. The invention adopts 1 - (2 - hydroxyethyl) -3 - (3 - bromopropyl) imidazole and dichlorosilane (IV) phthalocyanine to prepare di - (1 - (2 - ethoxy) -3 - (3 - bromopropyl) imidazole) axial substituted silicon phthalocyanine. .
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Paragraph 0016
(2021/10/05)
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- Matryoshka doll-type gold nanorod composite system loaded with novel sulfydryl N-heterocyclic silicon (IV) phthalocyanine complex
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The invention discloses a Matryoshka doll-type nano gold rod system loaded with di-(1-(4-hydroxyphenyl)-5-sulfydryl-tetrazolyl) silicon phthalocyanine as well as a preparation method and an application thereof. The preparation method comprises the following steps: firstly synthesizing a gold nanorod, then coating the surface of the gold nanorod with aminated silicon dioxide, and finally coating the surface of the gold nanorod with aminated silicon dioxide with a layer of gold nanospheres to prepare the Matryoshka doll-type gold nanorod with a three-layer cavity structure, enabling dichlorosilane phthalocyanine to react with 1-(4-hydroxyphenyl)-5-sulfydryl-tetrazole to synthesize di-(1-(4-hydroxyphenyl)-5-sulfydryl-tetrazole) silicon(IV)phthalocyanine; and finally, preparing a Matryoshka doll-type gold nanorod system loaded with di-(1-(4-hydroxyphenyl)-5-sulfydryl-tetrazolyl)silicon(IV)phthalocyanine and Matryoshka doll-type gold nanorods through a molecular assembly method, and takingthe Matryoshka doll-type gold nanorod system as photodynamic and photothermal therapy combined inactivation drug-resistant bacteria and tumors.
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Paragraph 0028-0029
(2020/08/18)
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- Prop-2-ynyloxybenzyloxy substituted phthalocyanine-based polymeric nanoparticles: synthesis, photophysical properties and in?vitro PDT efficacy
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Two prop-2-ynyloxybenzyloxy axially/peripherally substituted zinc/silicon phthalocyanines (YSiPc and YZnPc) were synthesized. They were encapsulated into an amphiphilic block copolymeric micelle polyethylene glycol monomethyl ether-polycaprolactone (MPEG5000–PCL2000) to form polymeric nanoparticles YSiPc@MPEG5000–PCL2000 and YZnPc@MPEG5000–PCL2000. The photophysical and photochemical properties of these polymeric nanoparticles were studied by UV/Vis and fluorescence spectroscopy. The cellular uptake and reactive oxygen species (ROS) production abilities of two polymeric nanoparticles in MCF-7 breast cancer cells were evaluated by confocal laser scanning imaging. YSiPc@MPEG5000–PCL2000 exhibited a higher cellular uptake, higher ROS generation ability as well as higher photodynamic efficacy against MCF-7 cells. YSiPc@MPEG5000–PCL2000 is a promising photosensitizer for photodynamic therapy.
- Xiao, Shuanghuang,Chen, Xiuqin,Ye, Qiuhao,Chen, Kuizhi,Xiao, Wenling,Guan, Xinqiao,Huang, Bingcheng,Liu, Guowei,Wei, Hui,Peng, Yiru
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p. 1232 - 1244
(2020/06/17)
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- Triphenylamine-based branch ligand substituted silicon phthalocyanine, preparation method and application thereof
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The invention discloses a triphenylamine-based branch ligand substituted silicon phthalocyanine, a preparation method and an application thereof. 4-bromotriphenylamine and 4-hydroxy phenylboronic acidare catalytically coupled through tetrakis (triphenylphosphine) palladium, so as to acquire a branch precursor 4'-(diphenyl amino)-[1,1'-biphenyl]-4-alcohol; the 4'-(diphenyl amino)-[1,1'-biphenyl]-4-alcohol (TPA-OH) reacts with SiPcCl2 in the presence of methylbenzene and K2CO3, so as to acquire bi-(4-(diphenyl amino)-1-biphenylyloxy) axially substituted silicon phthalocyanine; steric hindranceof a triphenylamine substituted branch structure is capable of restraining the gathering of phthalocyanine to some extent; the triphenylamine with an aggregation-induced emission characteristic is introduced into the branch structure, so that the 'aggregation-induced quenching' effect of phthalocyanine is improved, the optical physical property of phthalocyanine is regulated and the simultaneous execution of fluorescence imaging and photodynamic therapy is realized; the triphenylamine-based branch ligand substituted silicon phthalocyanine can be used as a fluorescence imaging agent and a photodynamic therapy photosensitizer.
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Paragraph 0017
(2019/01/08)
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- Silicon phthalocyanine substituted by trianilino fluoro aryl benzyl ether dendritic ligand and preparing method and application thereof
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The invention discloses silicon phthalocyanine substituted by a trianilino fluoro aryl benzyl ether dendritic ligand and a preparing method and application thereof. Firstly, 4'-(diphenylamino)-[1,1'-biphenyl]-4-carboxylic acid is synthesized from 4-bromotriphenylamine and phenylboronic acid, and is then subjected to condensation with hexafluorobisphenol A or bisphenol A respectively to prepare 4-(diphenylamino)-1-biphenylcarboxylic acid-1-carbobenzoxy-1,1,1,3,3,3-hexafluoropropyl phenol and 4-(diphenylamino)-1-biphenylcarboxylic acid-1-carbobenzoxy propyl phenol; and finally, the 4-(diphenylamino)-1-biphenylcarboxylic acid-1-carbobenzoxy-1,1,1,3,3,3-hexafluoropropyl phenol and the 4-(diphenylamino)-1-biphenylcarboxylic acid-1-carbobenzoxy propyl phenol react separately with silicon phthalocyanine dichloride to synthesize bis-(4-(diphenylamino)-1-biphenylcarboxylic acid-1-carbobenzoxy-4-(1,1,1,3,3,3-hexafluoropropyl-4-phenoxy) axially substituted silicon phthalocyanine and bis-(4-(diphenylamino)-1-biphenylcarboxylic acid-1-carbobenzoxypropylphenoxy) axially substituted silicon phthalocyanine. The products can be used as fluorescence imaging agents and photodynamic therapy photosensitizers.
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Paragraph 0019
(2019/01/08)
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- A double targeting phthalocyanine anticancer photosensitizer and its preparation method (by machine translation)
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The invention discloses a dual-target phthalocyanine anticancer photosensitizer and its preparation method, in the phthalocyanine parent ring in the axial direction to introduce [...] connected small molecular target drug N - (3 - chloro - 4 - fluorophenyl) - 7 - methoxy - 6 - (3 - morpholine - 4 - propoxy) quinazoline - 4 - amine, in order to improve its amphiphilic, biological compatibility and improved targeting of the photosensitizer; in the phthalocyanine parent ring in the axial direction of the other end into the triphenylphosphine group can make the photosensitizer selectively accurate intelligent positioning for the epidermal growth factor receptor (EGFR) over-expression of the mitochondria of tumor cells, improve the efficiency of the photodynamic effect. The structures of the compounds of a single, defined, does not exist isomers, the product is easy to separation and purification, at the same time the complex is not easy to assemble, help to improve the cell [...]. (by machine translation)
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Paragraph 0015
(2019/01/14)
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- Positively charged water-soluble arm type dendritic ligand silicon phthalocyanine complexes as well as preparation methods and application thereof
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The invention discloses positively charged water-soluble arm type dendritic ligand silicon phthalocyanine complexes as well as preparation methods and an application thereof. The complexes comprise di-(3,5-di(1',3'-methylpyridine propoxy)butanyloxy) axially substituted silicon phthalocyanine and di-(3,5-di(1',4'-isoquinoline butanyloxy)butanyloxy) axially substituted silicon phthalocyanine, wherein di-(3,5-di(1',3'-methylpyridine propoxy)butanyloxy) axially substituted silicon phthalocyanine is prepared from 3,5-di(1',3'-methylpyridine propoxy) phenyl methanol and silicon(IV) phthalocyanine dichloride or from 3,5-di-bromopropoxy) phenyl methanol and excessive methylpyridine and silicon(IV) phthalocyanine dichloride; di-(3,5-di(1',4'-isoquinoline butanyloxy)butanyloxy) axially substituted silicon phthalocyanine is prepared from 3,5-di(1',4'-quinoline butoxy) phenyl methanol and silicon(IV) phthalocyanine dichloride, or from 3,5-di(bromobutoxy) phenyl methanol and excessive isoquinoline and silicon(IV) phthalocyanine dichloride. The application of the complexes as a photosensitizer in photodynamic therapy is disclosed, especially the application to photoinactivation of MDRAB (multidrug-resistant acinetobacter baumannii).
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Paragraph 0031
(2018/03/24)
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- PHTHALOCYANINE PIGMENT, COLORING COMPOSITION AND COLOR FILTER
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PROBLEM TO BE SOLVED: To provide a phthalocyanine pigment that has excellent fastness (heat resistance, light fastness, solvent resistance) and, when used for a color filter or the like, is excellent in color properties (lightness) and the contrast ratio, without causing unusual matter due to association, aggregation or the like of molecules with each other even in a high temperature environment above 230°C. SOLUTION: The invention provides: a phthalocyanine pigment having a specific structure represented by general formula (1) or the like; and a coloring composition and a color filter using the phthalocyanine pigment. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0165
(2017/11/15)
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- COLORING COMPOUND AND INK, COLOR FILTER RESIST COMPOSITION, AND THERMAL TRANSFER RECORDING INK SHEET CONTAINING SAID COLORING COMPOUND
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The present invention provides a coloring compound that exhibits an excellent chromogenicity and provides an ink, a color filter resist composition, and a thermal transfer recording ink sheet that contain this coloring compound. The coloring compound has the structure represented by general formula (1), and the ink, color filter resist composition, and thermal transfer recording ink sheet contain this coloring compound.
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Paragraph 0042
(2014/03/25)
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- Production process for colorant, colorant composition, toner, ink for ink jet recording and color filter
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Provided is a production process for a colorant which contains a silicon phthalocyanine compound making it possible to reach a targeted particle diameter even by a conventional dispersing method and which is excellent in performances such as a color reproducibility, a light fastness, an electrostatic property, a transparency and the like, and a colorant composition, a toner, an ink for ink jet recording and a color filter which are excellent in the above performances. The above production process is a production process for a colorant containing a silicon phthalocyanine compound and a copper phthalocyanine compound and is characterized by having a preparing step of reacting raw materials of a silicon compound and phthalocyanine under the presence of a copper salt or the copper phthalocyanine compound described above to prepare the silicon phthalocyanine compound described above.
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Paragraph 0207
(2013/10/21)
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- PREPARATION OF SILICON PHTHALOCYANINES AND GERMANIUM PHTHALOCYANINES AND RELATED SUBSTANCES
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A process for preparing compounds of the general formula (I) by reacting the compound of the general formula (II) where L, L′ are the same or different and are each independently Cl or OH in the presence of a. chlorine compounds Cl-M2R1R2R3, Cl-M3R4R5R6, with the proviso that L and L′ are not both simultaneously OH, or b. hydroxyl compounds HO-M2R1R2R3, HO-M3R4R5R6. The use of compounds of the general formula (I) as markers for liquids and a process for detecting markers in liquids.
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Page/Page column 10
(2010/05/13)
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- Peripheral and axial substitution of phthalocyanines with solketal groups: Synthesis and in vitro evaluation for photodynamic therapy
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Phthalocyanines (Pcs) are a class of photosensitizers (PSs) with a strong tendency to aggregate in aqueous environment, which has a negative influence on their photosensitizing ability in photodynamic therapy. Pcs with either peripheral or axial solketal substituents, that is, ZnPc(sol)8 and Si(sol)2Pc, respectively, were synthesized and their tendency to aggregate as well as their photodynamic properties in 14C and B16F10 cell lines were evaluated. The results were compared to more hydrophilic silicon Pcs, that is, Si(PEG750)2Pc and Pc4. The order of cellular uptake was Pc4 > ZnPc(sol)8 > Si(PEG750)2Pc > Si(sol2)Pc. In contrast, Si(sol2)Pc showed the highest photocytotoxicity, while ZnPc(sol)8 did not show any photocytotoxicity up to a concentration of 10 μM in both cell types. UV/vis spectroscopy showed that Si(sol) 2Pc is less prone to aggregation than ZnPc(sol)8, which can explain the lack of photoactivity of the latter. Si(sol)2Pc was predominantly located in lipid droplets, whereas Si(PEG750)2Pc was homogeneously distributed in the cytosol, which is probably the main cause of their difference in photoactivity. The very high photodynamic efficacy of Si(sol)2Pc makes this PS an interesting candidate for future studies.
- Hofman, Jan-Willem,Van Zeeland, Femke,Turker, Selcan,Talsma, Herre,Lambrechts, Saskia A. G.,Sakharov, Dmitri V.,Hennink, Wim E.,Van Nostrum, Cornelus F.
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p. 1485 - 1494
(2008/02/01)
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- Phthalocyanine dyes
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Fluorescent dyes are disclosed which are useful as reporter groups for labeling biomolecules. The silicon phthalocyanine dyes disclosed are preferably water soluble, isomericly pure, possess high quantum yield, and are useful in bioassays.
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- Preparation and photophysical properties of halogenated silicon(IV) phthalocyanines substituted axially with poly(ethylene glycol) chains
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A series of silicon(IV) phthalocyanines with two axial poly(ethylene glycol) chains SiPcX8[(OCH2CH2)nOCH 3]2 (X=H, Cl, Br; n≈16) have been prepared of which the photosensitizing properties are enhanced as the periphery of the macrocycle is substituted with heavier halogens.
- Lo, Pui-Chi,Wang, Shuangqing,Zeug, Andre,Meyer, Matthias,R?der, Beate,Ng, Dennis K. P.
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p. 1967 - 1970
(2007/10/03)
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- Molecular metals based on silicon phthalocyanine complexes
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The complexes dichloro(phthalocyanino)silicon, [SiPcCl2], and bis(p- nitrophenoxy) (phthalocyanino) silicon, [SiPc(p-NPO)2] exhibit enhanced electrical properties on iodine doping. This may be due to the arrangement of the planar phthalocyanine molecules with decreased interplanar distance along with crystallographically similar environments and the presence of non integral formal oxidation state.
- Achar,Jayasree
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p. 1164 - 1168
(2007/10/03)
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- Electrophilic cleavage reactions of carbon-silicon bonds in neutral hexacoordinate silicon compounds: diorgano(phtalocyaninato)silicon
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Preparations of diorgano(phtalocyaninato)silicon 1)(R2)> and their reactions with N-bromosuccinimide (NBS), halogens, copper(II) halides, and 3-chloroperbenzoic acid (MCPBA) are reported.The alkyl-silicon bonds are readily cleaved by NBS, halogens, and CuX2 to give the corresponding alkyl halides.The reactivity of aryl-silicon bonds toward NBS and halogen depends greatly on the electronic effect of the substituent on the benzene ring, but these bonds are almost inert to CuX2.The reactivity of the carbon-silicon bond towards NBS cleavage decreases in the order 4-MeOC6H4 > n-C8H17 > 4-MeC6H4 > Ph >> 3-CF3C6H4.Cleavage of alkyl-silicon bonds may involv one-electron transfer from substrate to reagent and alkyl radical intermediates, while the electrophilic aromatic substitution mechanism may operate in the cleavage of aryl-silicon bonds. are stable to MCPBA.
- Tamao, Kohei,Akita, Munetaka,Kato, Hidehito,Kumada, Makoto
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p. 165 - 180
(2007/10/02)
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- Cofacial Assembly of Partially Oxidized Metallomacrocycles as an Approach to Controlling Lattice Architecture in Low-Dimensional Molecular Solids. Chemical and Architectural Properties of the "Face-to-Face" Polymers n, Where M = Si, Ge, and Sn
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This contribution reports a detailed chemical, spectroscopic, and X-ray diffractometric study of the nature and structure of the cofacially joined metallomacrocyclic polymers n, where M = Si, Ge, Sn and Pc = phtalocyaninato.These materials are precursors for a new class of electrically conductive polymers.Improved syntheses of the polymers are first reported.Optical spectra are assigned within the context of a porphyrinic "four orbital" model and related to those of the corresponding M(Pc)Cl2 and M(Pc)(OH)2 monomers.The vibrational spectra of the polymers are assigned, employing data from the aforementioned monomers and 18O substitution.Identification of the M-O stretching modes allows an estimation of the polymer molecular weights as a function of polymerization procedure via an end group analysis.Degrees of polymerization obtained for typical samples are n = 120 (30) (M = Si), 70 (40) (M = Ge), 100 (40) (M = Sn).A parallel, radiotracer determination employing labeled M(Pc)(O3H)2 monomers yields results in favorable agreement.It is found that n can be substantially varied by controlling the polymerization conditions.X-ray diffraction measerements show the n polymers to be highly crystalline.An analysis of the powder X-ray diffraction data has been carried out with carefully selected model compounds and computer simulation techniques.The results are in good accord with the proposed structure consisting of parallel chains of cofacially arrayed metallomacrocycles.The simplest structures which fit the experimental data are as follows: n, orthorhombic space group Ibam, a = 13.80 (5) Angstroem, b = 27.59 (5) Angstroem, c = 6.66 (4) Angstroem, Z = 4, interplanar spacing = 3.33 (2) Angstroem, intrastack phthalocyanine staggering angle = 39 (3) deg, density (g cm-3) = 1.458 (21) (calcd), 1.432 (10) (found); n, tetragonal space group P4/m, a = 13.27 (5) Angstroem, c = 3.53 (2) Angstroem, Z = 1, interplanar spacing = 3.53 (2) Angstroem, intrastack phthalocyanine staggering angle = 0 (5) deg, density (g cm-3) = 1.609 (29) (calcd), 1.512 (19) (found), or tetragonal space group I4/m, a = 18.76 (7) Angstroem, c = 3.53 (2) Angstroem, Z = 2, intrastack phthalocyanine staggering angle = 0 (5) deg, density (g cm-3) = 1.589 (26) (calcd), 1.512 (10) (found); n, tetragonal space group P4/m, a = 12.82 (2) Angstroem, c = 3.83 (2) Angstroem, Z = 1, intrastack phthalocyanine staggering angle ca. 0 deg, density (g cm-3) = 1.712 (25) (calcd), 1.719 (10) (found).The data for the latter structure are best fit to a model where the larger size of the Sn(IV) ion induces buckling of the macrocycle skeleton.An approximate analysis of the diffraction line widths suggests that crystallite dimensions are on the order of several hundred angstroms and are not grossly anisotropic.
- Dirk, Carl W.,Inabe, Tamotsu,Schoch, Karl F.,Marks, Tobin J.
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p. 1539 - 1550
(2007/10/02)
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