Novel columnar mesogen with octupolar optical nonlinearities: synthesis, mesogenic behavior and multiphoton-fluorescence-free hyperpolarizabilities of subphthalocyanines with long aliphatic chains†

Kang, SH; Kang, YS; Zin, WC; Olbrechts, Geert; Clays, Koen; Persoons, André; Kim, K

doi:10.1039/a904254g

Cited by 70 publications

(58 citation statements)

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“…[17] The UV/Vis spectra of subporphyrazines 2 a-d exhibit Soret and Q-bands at such energies that they reflect the lack of the three benzene rings with respect to the parallel subphthalocyanines. Thus, hexapropyl-(2 a,b) and hexathiopentyl-substituted (2 c,d) compounds display Q-bands at 501 and 559 nm, [17] respectively, that are blue-shifted by 70 [14a] and 43 nm [10] relative to similarly substituted SubPcs. Changes in the axial substitution pattern produce little to negligible effects in the electronic spectra of the macrocycles owing to the presence of nodes at the boron atoms both in the HOMO and LUMO orbitals of boronA C H T U N G T R E N N U N G (III) subporphyrazines.…”

Section: Resultsmentioning

confidence: 99%

“…For example, the subphthalocyanine periphery has been functionalized with groups of different nature to assemble subphthalocyanine-based p-extended oligomers, [8] or metallosupramolecular cages. [9] In other cases, materials showing mesomorphic behavior, [10] sensing abilities, [11] or LED applications, among others, were pursued. Very recently, other groups have reported related systems: the subporphyrins.…”

Section: Introductionmentioning

confidence: 99%

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Physicochemical Characterization of Subporphyrazines—Lower Subphthalocyanine Homologues

et al. 2009

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Physicochemical characterization of boron(III) subporphyrazines (SubPzs)--lower subphthalocyanine (SubPc) homologues--has been carried out for the first time. The SubPz macrocycle can act both as an oxidizing and a reducing entity, giving rise to stable radical anion or radical cation species, respectively. SubPzs are luminescent and exhibit fluorescence quantum yields that are in the range known for SubPcs. The peripheral substitution plays a dramatic role with respect to the luminescence properties. Moreover, as with SubPcs, deactivation of the singlet excited state of the SubPzs by intersystem crossing affords long-lived triplet excited states, which are amenable to being used as singlet-oxygen generators. Subporphyrazines are also promising electro- and photoactive materials for molecular photovoltaics.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Physicochemical Characterization of Subporphyrazines—Lower Subphthalocyanine Homologues

et al. 2009

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“…2) For bz(C24±C29) and bz(C36±C41(±y + 1, x ± y, z + 1/3)): centroid separation = 5.303 ; dihedral angle = 68.0. Since the discovery of sheet-curled chrysotile, [1] polypyrrole, [2] and carbon nanotubes, [3] organic and inorganic tubular materials have attracted much attention due to their unique physical and chemical properties.[4] Template-directed synthesis is widely accepted as a simple, high-throughput, and costeffective method for the fabrication of tubular fibers composed of metal sulfides and oxides, [5] metals, [6] or conducting polymers [7] through sol±gel polymerization, [8] electroless [9] or electrochemical [10] plating, or vapor deposition.[11] The inner surfaces of porous anodic alumina [12] and the outer surfaces of lipid-based cylindrical tubules, [13] organic gelator fibrils, [14] single-and double-headed amphiphile molecular assemblages, [15] carbon nanotubes, [16] and electrospun degradable polymer fibers [17] have been utilized as reliable templates for the fabrication of tubular fibers. Many efforts are currently being made to control the inner diameter and even the entire morphology of these tiny tubular materials.…”

mentioning

confidence: 99%

Tubular and Twisted Ni–P Fibers Molded from Morphology‐Tunable and Recyclable Organic Templates of Hydrogen‐Bonded Supramolecular Assemblages

Nakagawa¹,

Ishii

Aoki

et al. 2005

Advanced Materials

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distances relative to p±p interactions. Offset face to face p±p interactions: 1) For the benzene ring composed of carbon atoms C1 to C6 (bz(C1±C6)) and bz(C12±C17(±y + 1, x ± y, z + 1/3)): centroid separation = 4.832 ; dihedral angle = 25.7. 2) For bz(C1± C6) and bz(C1±C6(±y + 1, x ± y, z + 1/3, or ±x + y + 1, ±x + 1, z ± 1/3)): centroid separation = 5.115 ; dihedral angle = 7.97. 3) For bz(C12± C17) and bz(C36±C41(±x + y + 1, ±x + 1, z ± 1/3)): centroid separation = 5.464 ; dihedral angle = 4.96. Edge-to-face p±p interactions: 1) For bz (C12±C17) and bz(C24±C29(±y + 1, x ± y, z + 1/3)): centroid separation = 5.483 ; dihedral angle = 63.1. 2) For bz(C24±C29) and bz(C36±C41(±y + 1, x ± y, z + 1/3)): centroid separation = 5.303 ; dihedral angle = 68.0. Since the discovery of sheet-curled chrysotile, [1] polypyrrole, [2] and carbon nanotubes, [3] organic and inorganic tubular materials have attracted much attention due to their unique physical and chemical properties.[4] Template-directed synthesis is widely accepted as a simple, high-throughput, and costeffective method for the fabrication of tubular fibers composed of metal sulfides and oxides, [5] metals, [6] or conducting polymers [7] through sol±gel polymerization, [8] electroless [9] or electrochemical [10] plating, or vapor deposition.[11] The inner surfaces of porous anodic alumina [12] and the outer surfaces of lipid-based cylindrical tubules, [13] organic gelator fibrils, [14] single-and double-headed amphiphile molecular assemblages, [15] carbon nanotubes, [16] and electrospun degradable polymer fibers [17] have been utilized as reliable templates for the fabrication of tubular fibers. Many efforts are currently being made to control the inner diameter and even the entire morphology of these tiny tubular materials. We have reported previously that the amphoteric compound 6-[2-propyl-4-(4-pyridylazo)phenoxy]hexanoic acid (1, Fig. 1) self-organizes upon neutralization of its alkaline aqueous solution to give fibrous molecular assemblages.[18a] Atomic force microscopy (AFM) revealed that the dried fibrous molecular assemblages have an almost uniform submicrometer diameter of around 400 nm. During the neutralization, a COMMUNICATIONS 200

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“…Recognizing the need to drive solid-state organization in these electrically active materials, recent reports have detailed peripheral substitution of the SubPc core to induce self assembly in both solution and the solid state. [25][26][27][28] These reports, however, are limited to structural studies of these compounds; their charge-and energy transfer characteristics were not elucidated.…”

Section: Introductionmentioning

confidence: 99%

Self-Assembly of Axially Functionalized Subphthalocyanines in Thin Films

2015

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The addition of trialkoxylbenzyloxyl substituents at the axial position of conformationally non-planar SubPc promotes its solid-state self assembly. Unlike prior SubPc derivatives, photophysical studies suggest the presence of intermolecular electronic coupling between neighboring cores of SubPc derivatives, the strength of which depends on both the electronic nature of the core -which we tune through fluorination -and the extent of van der Waals interactions originating from the alkyl side chains on the trialkoxylbenzyloxyl tail. Modulating the relative strength of core-core and van der Waals interactions introduces morphological richness and provides access to liquid-crystalline hexagonal and smectic phases. When core-core interactions are strong, thin films of SubPc spontaneously adopt a highly crystalline lamellar structure in the solid state. Thin films of trialkoxylbenzyloxylsubstituted SubPcs thus support efficient energy and charge transfer given their intermolecular electronic communication and longrange order. INTRODUCTION:Guiding self-organization of organic π-conjugated molecules is essential to facilitate efficient charge and energy transfer in organic electronics. 1-6 To promote long range order, intermolecular interactions, such as ionic interactions, hydrogenbonding, π-π interactions, and van der Waals interactions, must work cooperatively to induce the spontaneous formation of hierarchical structures from basic molecular units. 7,8,9 Among organic π-conjugated molecules, conformationally non-planar systems are getting increasing attention in organic electronics. 10-13 Having a bowl-shaped conformation, subpthalocyanine (SubPc) is a special member of organic π-conjugated family. Derivatives of SubPc exhibit excellent photophysical properties, such as high absorptivity, high fluorescent quantum yield, and efficient charge/energy transfer, all of which have been exploited in areas of toxic anion sensing, two photo-absorption, and artificial photosynthetic systems. 14 SubPcs have also been successfully incorporated in high performance organic electronics, such as OLEDs, OFETs, and OPVs. 15-24 While SubPc crystals can form under stringent growth conditions, SubPc derivatives generally do not form ordered thin films, presumably because of the the non-planar conformation of the core. Given that charge transport in molecular semiconductors occurs via hopping, this lack of longrange order in SubPcs thin films is thought to limit the performance of devices that incorporate them. Recognizing the need to drive solid-state organization in these electrically active materials, recent reports have detailed peripheral substitution of the SubPc core to induce self assembly in both solution and the solid state. 25-28 These reports, however, are limited to structural studies of these compounds; their charge-and energy transfer characteristics were not elucidated.Different from previous reports, we have opted to axially functionalize SubPc with trialkoxylbenzyloxyl tails to drive assembly. As opposed to the phenoxyl ...

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Novel columnar mesogen with octupolar optical nonlinearities: synthesis, mesogenic behavior and multiphoton-fluorescence-free hyperpolarizabilities of subphthalocyanines with long aliphatic chains†

Cited by 70 publications

References 18 publications

Physicochemical Characterization of Subporphyrazines—Lower Subphthalocyanine Homologues

Physicochemical Characterization of Subporphyrazines—Lower Subphthalocyanine Homologues

Tubular and Twisted Ni–P Fibers Molded from Morphology‐Tunable and Recyclable Organic Templates of Hydrogen‐Bonded Supramolecular Assemblages

Self-Assembly of Axially Functionalized Subphthalocyanines in Thin Films

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