The .pi.-.pi. interactions and bandwidths in molecular metals. A chemical, structural, photoelectron spectroscopic, and Hartree-Fock-Slater study of monomeric and cofacially joined dimeric silicon phthalocyanines

Ciliberto, Enrico; Doris, K. A.; Pietro, William J.; Reisner, G. M.; Ellis, Donald E; Fragalá, Ignazio L.; Herbstein, F. H.; Ratner, Mark A.; Marks, Tobin J.

doi:10.1021/ja00337a018

Cited by 116 publications

(80 citation statements)

References 8 publications

(17 reference statements)

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“…The synthesis of the carbocyclic analogs, e.g., Pc(Nc) dichlorosilicon complexes, starting from the corresponding 1,3-diiminoisoindolines and silicon tetrachloride in tetrahydronaphthalene or quinoline, has previously been reported (1,13,29,30). In our hands, this procedure failed in the case of the heterocyclic diirninoisoindolines.…”

Section: Resultsmentioning

confidence: 86%

Substituted tetra-2,3-pyrazinoporphyrazines. Part II. Bis(tri-n-hexylsiloxy)silicon derivatives

Kudrevich¹,

Lier²

1996

Can. J. Chem.

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Dichlorosilicon complexes of substituted tetra-2,3-pyrazinoporphyrazines were obtained via condensation of 2,3-dicyanopyrazine, 2,3-dicyano-5,6-diphenylpyrazine, 2,3-dicyanoquinoxaline, 2,3-dicyano-benzoV]quinoxaline, and 2,3-dicyano-dibenzolf,h]quinoxaline with silicon tetrachloride in the presence of urea, quinoline, and tri-12-butylamine. Hydrolysis of the Si-C1 bond in concentrated H2S04, followed by treatment with 0.01 N NaOH and aqueous NH,, afforded the corresponding dihydroxides, which were converted to the bis(tri-n-hexylsiloxy)silicon derivatives via reaction with tri(nhexy1)silane in 3-picoline (2,4,6-collidine) in the presence of tri-n-butylamine. The axial tri-n-hexylsiloxy substituents at the central silicon atom prevent aggregation in organic solvents, permitting detailed studies on the effects of structural modifications on the electronic spectra of tetraazaphthalocyanines. Our data show that each benzo ring addition, angularly condensed to the tetra-2,3-quinoxalinoporphyrazine, induces a hypsochromic shift (-10-15 nm) of the main absorption maximum.Key words: phthalocyanine, aza analog, bis(tri-n-hexylsiloxy)silicon complex.Resume : Les dtrivts substituts des tttra-2,3-pyrazinoporphyrazines du dichlorosilice ont t t t prtparts via la condensation du 2.3-dicyanopyrazine, 2,3-dicyano-5,6-diphenylpyrazine, 2,3-dicyanoquinoxaline, 2,3-dicyano-benzoV]quinoxaline et 2.3-dicyano-dibenzoV;h]quinoxaline avec du tttrachlorure de silice en presence d'urte, de quinoltine et d'amine tri-n-butylique. L'hydrolyse de liaison Si-C1 dans du H,S04 concentrt, puis dans une solution de 0,01 N de NaOH et d'ammoniac, a produit des dihydroxydes appropriCs qui ont CtC transformts en dtrivts substituts de bis(tri-12-hexylsiloxy) via la reaction avec le tri-n-hexylsilane dans la 3-picoline (2,4,6-collidine) en prtsence d'amine tri-n-butylique. Les substituants axiaux tri-11-hexylsiloxy, attachts h l'atome de silicium central, empkchent complktement l'agrtgation des moltcules d'azaphtalocyanines dans les solvants organiques. Des etudes dttailltes de l'influence de la modification structurelle sur les spectres Clectroniques du tttraazaphtalocyanine ont ttC effectutes. I1 a CtC dtmontrt que chaque anneau benzo angulaire, condenst au tttra-2,3-quinoxalinoporphyrazine, produit un dtplacement hypsochromique (-10-15 nm) de la bande Q.Mots clis : phtalocyanine, azaanalogue, complexe du bis(tri-n-hexylsi1oxy)silice.

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Section: Resultsmentioning

confidence: 86%

Substituted tetra-2,3-pyrazinoporphyrazines. Part II. Bis(tri-n-hexylsiloxy)silicon derivatives

Kudrevich¹,

Lier²

1996

Can. J. Chem.

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“…Nevertheless, these values evidently show the efficient generation of 1 О 2 , particularly for titanyl phthalocyanines with Ф ∆ ~ 0.5. For LZn efficacy of 1 O 2 generation (Ф ∆ 0.4) was slightly lower than typical values for zinc phthalocyanines in monomer form (Ф ∆ 0.6-0.7) [21] because of partial aggregation at pH 9.5. Lowering pH value to 8.5 increases the degree of LZn aggregation, leading to the decrease of Ф ∆ to 0.15.…”

Section: At the Same Time A Noticeable Decrease Of Laloh Andmentioning

confidence: 67%

“…As a result, at pH 12 molar extinction coefficients of complexes are rather high (Table 1) except for LTiO and LSiCl 2 , which at high pH can form linear oligomers through oxygen at central atom of type -Si-O-Si-О. [21] When changing pH from 12 to 8.5, electronic absorption spectra of LSiCl 2 , LAlOH and LGaOH, which contain axial ligand, retain the character typical to the monomeric state.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Some Properties of Phosphonomethyl Substituted Phthalocyanines

Komissarov¹,

Макаров²,

Yuzhakova³

et al. 2012

MHC

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“…It is important to note that the 1082 previously reported phthalocyanine monomers and dimers derived from monofunctional alcohols such as Si[C(CH 3 h](CH3) 2 OH were soluble only in basic organic solvents such as pyridine and quinoline, and somewhat less soluble in polar solvents such as chloroform and dioxane. 20 The most interesting feature of these derivatives is their facile processability into thin polyurethane films. The hydroxyl groups of these Pc derivatives react with a reactive diisocyanate compound such as isophorone diisocyanate to form urethane linkages.…”

Section: Resultsmentioning

confidence: 99%

“…Interestingly, Q-and B-band transitions of the dimers showed a dramatic shift to the blue region relative to the monomers, due to excitation coupling of neutral excitation transition between the Pc rings of the dimer. 20 …”

Section: Resultsmentioning

confidence: 99%

Thin Polyurethane Films of Polyhydroxysilicon Phthalocyanine and Bis-phthalocyanine Derivatives

Sinha

Mandal

1995

Polym J

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ABSTRACT:A series of new silicon phthalocyanine [SiPc(OR),] and silicon bis-phthalocyanine [RO(SiPcO),R] derivatives containing two or more hydroxyl groups was synthesized by axial etherification of [PcSi(OH)2] or [HO(SiPcO),H] with various polyfunctional alcohols, where R is a residue generated from the corresponding alcohol namely, triethanolamine, triethylene glycol or N, N-bis(2-hydroxyethyl isonicotinamide). These derivatives can be processed into thin polymeric films by reacting with isophorone diisocyanate. Many of the derivatives demonstrated high solubility in common organic solvents such as chloroform and dioxane, and exhibit low absorptions in the visible region.KEY WORDS Polyhydroxysilicon Phthalocyanine and Bis-phthalocyanine / Third-Order Nonlinear Optical Properties / Polyurethane / Phthalocyanine (Pc) derivatives have emerged as one of the most promising classes of materials in the area of nonlinear optics due to their large and ultrafast third-order optical nonlinearities. 1 -3 Although the molecular design requirements for practical third-order nonlinear optical materials are poorly understood, a combination of long n-conjugation length and low HOMO-LUMO gaps appear important. We and others have been interested in developing prototype devices for the protection of vision and sensors against short, intense laser pulses using Pc compounds due to their favorable transparency in the visible spectral range. 4 -7 To provide efficient vision protection, a material should possess (i) high nonresonant nonlinear optical susceptibility, l 3 l, which is directly proportional to the number density of the n-conjugated molecules (ii) be easily processable into thin films and (iii) be optically transparent in the visible region. However, the practical applicability of many

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The .pi.-.pi. interactions and bandwidths in molecular metals. A chemical, structural, photoelectron spectroscopic, and Hartree-Fock-Slater study of monomeric and cofacially joined dimeric silicon phthalocyanines

Cited by 116 publications

References 8 publications

Substituted tetra-2,3-pyrazinoporphyrazines. Part II. Bis(tri-n-hexylsiloxy)silicon derivatives

Substituted tetra-2,3-pyrazinoporphyrazines. Part II. Bis(tri-n-hexylsiloxy)silicon derivatives

Synthesis and Some Properties of Phosphonomethyl Substituted Phthalocyanines

Thin Polyurethane Films of Polyhydroxysilicon Phthalocyanine and Bis-phthalocyanine Derivatives

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