The synthetic quest for ‘splendid isolation’ within phthalocyanine materials

Brewis, Matthew; Hassan, Bashir M.; Li, Hong; Makhseed, Saad; McKeown, Neil B.; Thompson, Neil

doi:10.1002/1099-1409(200008)4:5<460::aid-jpp262>3.3.co;2-c

Cited by 14 publications

(24 citation statements)

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“…Because these pseudorotaxanes lack one blocking group along the linear portion, the threading and dethreading equilibrium is subject to environmental conditions. Porphyrins 72,143,146,164,[243][244][245][246][247][248][249][250][251][252][253][254][255][256][257][258][259] and the closely related phthalocyanines [260][261][262][263][264][265][266][267] have been utilized extensively as dendrimer cores because of their interesting electrical, optical, and catalytic properties. Inoue and co-workers reported the first convergent synthesis of a porphyrin-core dendrimer 248 by attaching poly(aryl ether) dendrons onto the preformed porphyrin 172.…”

Section: A Traditional Covalently Bound Coresmentioning

confidence: 99%

Convergent Dendrons and Dendrimers: from Synthesis to Applications

2001

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I. Introduction 3819 A. Structure 3820 B. Applications 3821 C. Synthetic Approaches 3821 1. Divergent Approach 3821 2. Convergent Approach 3822 D. Features of the Convergent Synthesis 3823 1. Structural Purity 3823 2. Synthetic Versatility 3823 II. Convergent Synthesis of Dendrons and Dendrimers 3824 A. Single-Stage Convergent Syntheses 3824 1. Poly(aryl ether) Dendrimers 3824 2. Poly(aryl alkyne) Dendrimers 3826 3. Poly(phenylene) Dendrimers 3827 4. Poly(alkyl ester) Dendrimers 3827 5. Poly(aryl alkene) Dendrimers 3828 6. Poly(alkyl ether) Dendrimers 3828 7. Other Convergent Dendrimer Syntheses 3829 B. Accelerated Approaches 3829 1.

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Section: A Traditional Covalently Bound Coresmentioning

confidence: 99%

Convergent Dendrons and Dendrimers: from Synthesis to Applications

2001

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“…Ivanov et al reported that intracolumnar stacking distance can be reduced to 3.18 Å by using intermolecular hydrogen bonding of the peripheral chains [9]. Moreover, it has recently been reported in the field of non-liner optical materials that the substituent positions change the intermolecular interaction [10][11][12][13][14][15][16]. Hence, this suggests that the peripheral chain positions of discotic liquid crystals may also change their intermolecular interactions.…”

Section: Introductionmentioning

confidence: 99%

Discotic liquid crystals of transition metal complexes 38^†: peripheral chain substituent position effect on columnar mesophase and stacking structures of novel phthalocyanine-based liquid crystals

Ichihara

Suzuki

Hatsusaka

et al. 2007

J. Porphyrins Phthalocyanines

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In order to clarify the peripheral chain substitution position effect on columnar mesophase and stacking structures, we have synthesized three novel series of discotic liquid crystals (1-3) having octakis(phenoxy)phthalocyaninato copper(II) as a central core and one peripheral chain at the para position (1), meta position (2) or ortho position (3) of each phenoxy group, and three more novel series of discotic liquid crystals (4-6) having the same central core and two peripheral chains at para and meta positions (4), meta and meta positions (5) or ortho and meta positions (6) of each phenoxy group. Their columnar mesophase and stacking structures were investigated with a polarizing optical microscope, a differential scanning calorimeter and a temperature-dependent X-ray diffractometer. According to the results, their columnar mesophase and stacking structures strongly depended on the peripheral chain substitution positions and the number of peripheral chains. Derivatives 3 and 5 are viscous isotropic liquid at room temperature. Derivatives 1, 2, 4 and 6 exhibit various kinds of columnar mesophases: 1 Col hd ; 2 Col hd and Col ho ; 4 Col hd , Col rd (P2 1 /a), Col tet.d and Cub(Pn[three bar]m); 6 Col hd , Col rd (P2 1 /a) and Col rd (X). Moreover, derivatives 1, 4 and 6 exhibit disordered columnar mesophases. However, derivative 2 only exhibits an ordered columnar mesophase and its X-ray diffraction pattern shows a sharp reflection corresponding to a very short intracolumnar stacking distance of 3.33 Å. Thus, we can drastically change the mesophase and stacking structures by the peripheral chain substitution positions and the number of peripheral chains at each phenoxy group. This is a new way of controlling mesomorphic structure.

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“…For this reason we first attempted to add substoichiometric quantities of ZnPc to HP7 which had a single heme bound, at the Histidine 42 site (Koder et al, 2009). As Figure 2 demonstrates, even at ZnPc to HP7 ratios as low as 1 to 10 the ZnPc molecules bind at this site in a stacked dimeric configuration as identified by the exciton coupled peak at 630 nm(Brewis et al, 2000). Binding was confirmed by the fact that the heterocomplex passed through a size exclusion column intact, and the retention time indicates that the heterocomplex is not oligomerized (not shown).…”

Section: Resultsmentioning

confidence: 99%

“…To take full advantage of their superior spectrochemical properties phthalocyanines must be maintained in ‘splendid isolation’, avoiding their assembly into cofacial aggregates (Brewis et al, 2000). Simple modifications such as macrocycle sulfonation, while making monomeric phthalocyanines more soluble in hydrophilic solvents, do little to inhibit the progressive accumulation of stacked phthalocyanines as the cofacial stacking interaction is highly favorable energetically.…”

Section: Introductionmentioning

confidence: 99%

Rational design of a zinc phthalocyanine binding protein

Mutter¹,

Norman²,

Tiedemann³

et al. 2014

Journal of Structural Biology

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Phthalocyanines have long been used as primary donor molecules in synthetic light-powered devices due to their superior properties when compared to natural light activated molecules such as chlorophylls. Their use in biological contexts, however, has been severely restricted due to their high degree of self-association, and its attendant photoquenching, in aqueous environments. To this end we report the rational redesign of a de novo four helix bundle di-heme binding protein into a heme and Zinc(II) phthalocyanine (ZnPc) dyad in which the ZnPc is electronically and photonically isolated. The redesign required transformation of the homodimeric protein into a single chain four helix bundle and the addition of a negatively charge sulfonate ion to the ZnPc macrocycle. To explore the role of topology on ZnPc binding two constructs were made and the resulting differences in affinity can be explained by steric interference of the newly added connecting loop. Singular binding of ZnPc was verified by absorption, fluorescence, and magnetic circular dichroism spectroscopy. The engineering guidelines determined here, which enable the simple insertion of a monomeric ZnPc binding site into an artificial helical bundle, are a robust starting point for the creation of functional photoactive nanodevices.

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The synthetic quest for ‘splendid isolation’ within phthalocyanine materials

Cited by 14 publications

References 0 publications

Convergent Dendrons and Dendrimers: from Synthesis to Applications

Convergent Dendrons and Dendrimers: from Synthesis to Applications

Discotic liquid crystals of transition metal complexes 38^†: peripheral chain substituent position effect on columnar mesophase and stacking structures of novel phthalocyanine-based liquid crystals

Rational design of a zinc phthalocyanine binding protein

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The synthetic quest for ‘splendid isolation’ within phthalocyanine materials

Cited by 14 publications

References 0 publications

Convergent Dendrons and Dendrimers: from Synthesis to Applications

Convergent Dendrons and Dendrimers: from Synthesis to Applications

Discotic liquid crystals of transition metal complexes 38†: peripheral chain substituent position effect on columnar mesophase and stacking structures of novel phthalocyanine-based liquid crystals

Rational design of a zinc phthalocyanine binding protein

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Discotic liquid crystals of transition metal complexes 38^†: peripheral chain substituent position effect on columnar mesophase and stacking structures of novel phthalocyanine-based liquid crystals