Systematic extension of the length of the organic conjugated π-system of mesoporous silica-based organic–inorganic hybrid materials

Cornelius, Maximilian; Hoffmann, Frank; Ufer, Boris; Behrens, Peter; Fröba, Michael

doi:10.1039/b801034j

Cited by 37 publications

(22 citation statements)

References 22 publications

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“…Mesostructured and mesoporous organosilica materials have attracted much attention because of their high applicability to optical materials, electronic devices, adsorbents, solid catalysts, and biomedical uses . The covalent inorganic–organic hybrid framework with mesostructures is constructed by surfactant‐directed polycondensation of bridged organosilane precursors (R[Si(OR′) 3 ] n ; n ≥ 2).…”

Section: Introductionmentioning

confidence: 99%

“…Mesostructured and mesoporous organosilica materials have attracted much attention because of their high applicability to optical materials, electronic devices, adsorbents, solid cata lysts, and biomedical uses. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] The covalent inorganic-organic hybrid framework with mesostructures is constructed by sur factantdirected polycondensation of bridged organosilane precursors (R[Si(OR′) 3 ] n ; n ≥ 2). Functionalization of meso structured organosilicas is achievable in various ways, such as tuning of the composition of the organosilica framework, chemical surface modification of the pore walls, and introduc tion of guest materials into the mesopores.…”

Section: Introductionmentioning

confidence: 99%

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Enhanced Photoluminescence of Mesostructured Organosilica Films with a High Density of Fluorescent Chromophores

Mizoshita

Inagaki

2018

Macro Chemistry & Physics

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Synthesis of mesostructured materials containing a high density of organic chromophores in the frameworks is highly desired for applications in unique optical devices using energy transfer. However, a dense accumulation of fluorescent chromophores in solid form generally causes concentration quenching. In this study, dense embedding of the chromophore 1,6‐diphenylpyrene within the framework of mesostructured organosilica films results in efficient blue fluorescence emission with high quantum yields of over 0.75. In contrast to conventional fluorescent films where chromophores are diluted and isolated to suppress concentration quenching, increasing the density of 1,6‐diphenylpyrene moieties within the mesostructured framework leads to the efficient formation of highly emissive excimers. Mesostructured frameworks achieving both high light‐absorptivity and efficient fluorescence emission have great potential in light‐emitting materials, fluorescence sensors, and light‐harvesting components for photoluminescent and photocatalytic systems.

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“…Mesostructured and mesoporous organosilica materials have attracted much attention because of their high applicability to optical materials, electronic devices, adsorbents, solid catalysts, and biomedical uses . The covalent inorganic–organic hybrid framework with mesostructures is constructed by surfactant‐directed polycondensation of bridged organosilane precursors (R[Si(OR′) 3 ] n ; n ≥ 2).…”

Section: Introductionmentioning

confidence: 99%

“…Mesostructured and mesoporous organosilica materials have attracted much attention because of their high applicability to optical materials, electronic devices, adsorbents, solid cata lysts, and biomedical uses. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] The covalent inorganic-organic hybrid framework with mesostructures is constructed by sur factantdirected polycondensation of bridged organosilane precursors (R[Si(OR′) 3 ] n ; n ≥ 2). Functionalization of meso structured organosilicas is achievable in various ways, such as tuning of the composition of the organosilica framework, chemical surface modification of the pore walls, and introduc tion of guest materials into the mesopores.…”

Section: Introductionmentioning

confidence: 99%

Enhanced Photoluminescence of Mesostructured Organosilica Films with a High Density of Fluorescent Chromophores

Mizoshita

Inagaki

2018

Macro Chemistry & Physics

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“…Various organic bridges R ranging from functional p systems to metal complexes are available for tailoring functional frameworks with particular properties, such as tuning of HOMO-LUMO levels, fixation of electroactive organic groups, and formation of reactive and catalytic sites. [7][8][9][10][11][12] One of the most remarkable features of PMOs is the induction of molecular-scale periodicity in the pore wall, which has been realized for PMOs synthesized from dipodal rod-like precursors with rigid p-conjugated aromatic bridges (for example, 1,4-phenylene and 4,4'-biphenylylene) under basic hydrolytic conditions (Figure 1 a, left). [13][14][15][16][17][18][19][20] Molecularscale "crystal-like" ordering of the framework should enable design and control of the optical, electrical, and surface properties of PMOs.…”

mentioning

confidence: 99%

Mesoporous Organosilica Hybrids Consisting of Silica‐Wrapped π–π Stacking Columns

et al. 2011

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Periodic mesoporous organosilica (PMO) materials prepared by surfactant-directed polycondensation of bridged organosilane precursors (R[Si(OR') 3 ] n ; n ! 2, R = organic bridging groups, R' = methyl, ethyl, etc.) are a new class of functional porous hybrid materials. [1][2][3][4][5][6] Organic groups R can be densely embedded within the pore walls without plugging the mesopores. Various organic bridges R ranging from functional p systems to metal complexes are available for tailoring functional frameworks with particular properties, such as tuning of HOMO-LUMO levels, fixation of electroactive organic groups, and formation of reactive and catalytic sites. [7][8][9][10][11][12] One of the most remarkable features of PMOs is the induction of molecular-scale periodicity in the pore wall, which has been realized for PMOs synthesized from dipodal rod-like precursors with rigid p-conjugated aromatic bridges (for example, 1,4-phenylene and 4,4'-biphenylylene) under basic hydrolytic conditions (Figure 1 a, left). [13][14][15][16][17][18][19][20] Molecularscale "crystal-like" ordering of the framework should enable design and control of the optical, electrical, and surface properties of PMOs. However, all of the conventional crystallike PMOs show lamellar structures consisting of alternating organic and silica layers (Figure 1 a, left). [13][14][15][16][17][18][19][20] In this configuration, the distance between neighboring organic bridges is about 0.44 nm, which is much longer than typical face-to-face p-p stacking distances (0.34-0.36 nm); [21,22] therefore, neither strong electronic coupling nor significant electroconductive properties are expected for the pore walls. The lamellar arrangement is thought to be directed by a hydrophobichydrophilic interaction of fully hydrolyzed dipodal precursors ((HO) 3 SiÀRÀSi(OH) 3 ) and subsequent polycondensation; the position and distance of the organic bridges are restricted by the chemical bond length of the siloxane network.Herein we present the first synthesis of a new class of molecularly ordered PMOs with columnar stacking of the bridging organic groups with a face-to-face p-stacking distance of 0.35-0.36 nm (Figure 1 a, right). The new PMOs were synthesized by surfactant-directed polycondensation of newly designed disk-like alkoxysilane precursors with hydrophobic and electroactive perylene bisimide (PBI) [22] cores (Figure 1 b). The key to the formation of this new type of the ordered structure is full utilization of the p-p stacking nature of the hydrophobic PBI moieties rather than the hydrophobic-hydrophilic interaction. As shown in Figure 1 c, the formation of mesostructured hybrids consisting of p-stacked PBI columns and micellar aggregates of a cationic surfactant is promoted under basic hydrolytic conditions through columnar self-assembly of disk-like PBI precursors and electrostatic interaction between the cationic surface of the micelles and the anionic silanolate groups of the columnassembled precursors. The PBI columns are then wrapped and reinforced with a pur...

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“…[17a] Expansion of the aromatic and p-conjugated organic bridges has led to a red shift of the absorption bands and resulted in efficient fluorescence emission in the visible-light region. [17][18][19] These recent developments can broaden the potential applications of periodic mesostructured organosilicas as visible-light-responsive photofunctional materials.Well-defined mesostructures are also appropriate for the confinement of dyes, [20][21][22] suggesting the versatility of mesostructured materials for luminescence and efficient energy transfer. We recently reported efficient fluorescence resonance energy transfer (FRET) from an organosilica framework to a fluorescent dye incorporated into the mesopores, which occurred in coumarin-doped biphenyl-silica mesoporous materials.…”

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confidence: 99%

Efficient Visible‐Light Emission from Dye‐Doped Mesostructured Organosilica

et al. 2009

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Efficient and color‐tunable visible‐light emission is achieved in fluorescent dye‐doped oligo(phenylenevinylene)–silica mesostructured films through fluorescence resonance energy transfer from a blue‐light‐emitting organosilica to a yellow‐light‐emitting dye (see figure). Tuning of the composition realizes pseudo white‐light emission with a quantum yield of 67%. Utilization of both walls and pores of the mesostructured organosilicas is effective to construct highly functional systems.

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Systematic extension of the length of the organic conjugated π-system of mesoporous silica-based organic–inorganic hybrid materials

Cited by 37 publications

References 22 publications

Enhanced Photoluminescence of Mesostructured Organosilica Films with a High Density of Fluorescent Chromophores

Enhanced Photoluminescence of Mesostructured Organosilica Films with a High Density of Fluorescent Chromophores

Mesoporous Organosilica Hybrids Consisting of Silica‐Wrapped π–π Stacking Columns

Efficient Visible‐Light Emission from Dye‐Doped Mesostructured Organosilica

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