Directed organization of dye aggregates in hydrogen-bonded host frameworks

Airon C. Soegiarto, Michael Ward

Research output: Contribution to journalArticle

Abstract

Organic laser dyes coumarin 1, coumarin 2, coumarin 102, coumarin 314, and coumarin 334 have been included in crystalline guanidinium organodisulfonate (GDS) host frameworks, forming stable inclusion compounds with lamellar architectures. The GDS hosts consist of 2D quasihexagonal hydrogen-bonded sheets with topologically complementary guanidinium (G) ions and the sulfonate (S) moieties of a variety of organodisulfonates that serve as "pillars" that connect opposing GS sheets, thus generating inclusion cavities between the sheets. These host frameworks display a variety of architectural isomers, including the so-called bilayer, simple brick, zigzag brick as well as two heretofore unreported framework isomers: double zigzag brick and a "chevron" brick. These isomers vary with respect to the connectivity between opposing GS sheets and the corresponding shape of the inclusion cavities. The preference for the framework isomers reflects a systematic templating role for the guest molecules, largely based on their steric requirements. The coumarin guests exhibit a distinct arrangement in each host-guest combination, resulting in a range of fluorescence emission wavelengths that differ from that observed for the monomeric form in dilute solutions. For example, the bilayer framework, which has narrow 1D pores, enforces the alignment of coumarin guests as head-to-tail arrays resembling J-aggregates. The simple brick structure, however, has wider 1D channels that permit the formation of linear arrays of face-to-face coumarin dimers resembling H-aggregates. The coumarin guests in the zigzag brick architecture are confined within isolated inclusion cavities as face-to-face dimers. In general, the maxima of the emission bands of the coumarin dyes in the bilayer structure are blue-shifted, while those in the simple brick and zigzag brick structures are red-shifted. The fluorescence reflects the unique guest-guest packing in each framework isomer as well as interactions between the coumarin guest and the organodisulfonate pillar. The ability to include laser dyes in high concentrations in a robust host framework with regulation of intermolecular association between the dye molecules may lead to new solid-state lasing materials that overcome some of the barriers encountered for dyes embedded as dilute solutes in amorphous solid-state matrices such as polymers, zeolites, and sol-gel glasses.

Original languageEnglish (US)
Pages (from-to)3803-3815
Number of pages13
JournalCrystal Growth and Design
Volume9
Issue number8
DOIs
StatePublished - Aug 5 2009

Fingerprint

bricks
Brick
Hydrogen
Coloring Agents
Dyes
dyes
Isomers
hydrogen
isomers
inclusions
Guanidine
Dimers
cavities
Organic lasers
Fluorescence
dimers
organic lasers
solid state
fluorescence
Molecules

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

Cite this

Directed organization of dye aggregates in hydrogen-bonded host frameworks. / Soegiarto, Airon C.; Ward, Michael.

In: Crystal Growth and Design, Vol. 9, No. 8, 05.08.2009, p. 3803-3815.

Research output: Contribution to journalArticle

@article{c95cff001c4045d59dca45406618d38f,
title = "Directed organization of dye aggregates in hydrogen-bonded host frameworks",
abstract = "Organic laser dyes coumarin 1, coumarin 2, coumarin 102, coumarin 314, and coumarin 334 have been included in crystalline guanidinium organodisulfonate (GDS) host frameworks, forming stable inclusion compounds with lamellar architectures. The GDS hosts consist of 2D quasihexagonal hydrogen-bonded sheets with topologically complementary guanidinium (G) ions and the sulfonate (S) moieties of a variety of organodisulfonates that serve as {"}pillars{"} that connect opposing GS sheets, thus generating inclusion cavities between the sheets. These host frameworks display a variety of architectural isomers, including the so-called bilayer, simple brick, zigzag brick as well as two heretofore unreported framework isomers: double zigzag brick and a {"}chevron{"} brick. These isomers vary with respect to the connectivity between opposing GS sheets and the corresponding shape of the inclusion cavities. The preference for the framework isomers reflects a systematic templating role for the guest molecules, largely based on their steric requirements. The coumarin guests exhibit a distinct arrangement in each host-guest combination, resulting in a range of fluorescence emission wavelengths that differ from that observed for the monomeric form in dilute solutions. For example, the bilayer framework, which has narrow 1D pores, enforces the alignment of coumarin guests as head-to-tail arrays resembling J-aggregates. The simple brick structure, however, has wider 1D channels that permit the formation of linear arrays of face-to-face coumarin dimers resembling H-aggregates. The coumarin guests in the zigzag brick architecture are confined within isolated inclusion cavities as face-to-face dimers. In general, the maxima of the emission bands of the coumarin dyes in the bilayer structure are blue-shifted, while those in the simple brick and zigzag brick structures are red-shifted. The fluorescence reflects the unique guest-guest packing in each framework isomer as well as interactions between the coumarin guest and the organodisulfonate pillar. The ability to include laser dyes in high concentrations in a robust host framework with regulation of intermolecular association between the dye molecules may lead to new solid-state lasing materials that overcome some of the barriers encountered for dyes embedded as dilute solutes in amorphous solid-state matrices such as polymers, zeolites, and sol-gel glasses.",
author = "Soegiarto, {Airon C.} and Michael Ward",
year = "2009",
month = "8",
day = "5",
doi = "10.1021/cg900578u",
language = "English (US)",
volume = "9",
pages = "3803--3815",
journal = "Crystal Growth and Design",
issn = "1528-7483",
publisher = "American Chemical Society",
number = "8",

}

TY - JOUR

T1 - Directed organization of dye aggregates in hydrogen-bonded host frameworks

AU - Soegiarto, Airon C.

AU - Ward, Michael

PY - 2009/8/5

Y1 - 2009/8/5

N2 - Organic laser dyes coumarin 1, coumarin 2, coumarin 102, coumarin 314, and coumarin 334 have been included in crystalline guanidinium organodisulfonate (GDS) host frameworks, forming stable inclusion compounds with lamellar architectures. The GDS hosts consist of 2D quasihexagonal hydrogen-bonded sheets with topologically complementary guanidinium (G) ions and the sulfonate (S) moieties of a variety of organodisulfonates that serve as "pillars" that connect opposing GS sheets, thus generating inclusion cavities between the sheets. These host frameworks display a variety of architectural isomers, including the so-called bilayer, simple brick, zigzag brick as well as two heretofore unreported framework isomers: double zigzag brick and a "chevron" brick. These isomers vary with respect to the connectivity between opposing GS sheets and the corresponding shape of the inclusion cavities. The preference for the framework isomers reflects a systematic templating role for the guest molecules, largely based on their steric requirements. The coumarin guests exhibit a distinct arrangement in each host-guest combination, resulting in a range of fluorescence emission wavelengths that differ from that observed for the monomeric form in dilute solutions. For example, the bilayer framework, which has narrow 1D pores, enforces the alignment of coumarin guests as head-to-tail arrays resembling J-aggregates. The simple brick structure, however, has wider 1D channels that permit the formation of linear arrays of face-to-face coumarin dimers resembling H-aggregates. The coumarin guests in the zigzag brick architecture are confined within isolated inclusion cavities as face-to-face dimers. In general, the maxima of the emission bands of the coumarin dyes in the bilayer structure are blue-shifted, while those in the simple brick and zigzag brick structures are red-shifted. The fluorescence reflects the unique guest-guest packing in each framework isomer as well as interactions between the coumarin guest and the organodisulfonate pillar. The ability to include laser dyes in high concentrations in a robust host framework with regulation of intermolecular association between the dye molecules may lead to new solid-state lasing materials that overcome some of the barriers encountered for dyes embedded as dilute solutes in amorphous solid-state matrices such as polymers, zeolites, and sol-gel glasses.

AB - Organic laser dyes coumarin 1, coumarin 2, coumarin 102, coumarin 314, and coumarin 334 have been included in crystalline guanidinium organodisulfonate (GDS) host frameworks, forming stable inclusion compounds with lamellar architectures. The GDS hosts consist of 2D quasihexagonal hydrogen-bonded sheets with topologically complementary guanidinium (G) ions and the sulfonate (S) moieties of a variety of organodisulfonates that serve as "pillars" that connect opposing GS sheets, thus generating inclusion cavities between the sheets. These host frameworks display a variety of architectural isomers, including the so-called bilayer, simple brick, zigzag brick as well as two heretofore unreported framework isomers: double zigzag brick and a "chevron" brick. These isomers vary with respect to the connectivity between opposing GS sheets and the corresponding shape of the inclusion cavities. The preference for the framework isomers reflects a systematic templating role for the guest molecules, largely based on their steric requirements. The coumarin guests exhibit a distinct arrangement in each host-guest combination, resulting in a range of fluorescence emission wavelengths that differ from that observed for the monomeric form in dilute solutions. For example, the bilayer framework, which has narrow 1D pores, enforces the alignment of coumarin guests as head-to-tail arrays resembling J-aggregates. The simple brick structure, however, has wider 1D channels that permit the formation of linear arrays of face-to-face coumarin dimers resembling H-aggregates. The coumarin guests in the zigzag brick architecture are confined within isolated inclusion cavities as face-to-face dimers. In general, the maxima of the emission bands of the coumarin dyes in the bilayer structure are blue-shifted, while those in the simple brick and zigzag brick structures are red-shifted. The fluorescence reflects the unique guest-guest packing in each framework isomer as well as interactions between the coumarin guest and the organodisulfonate pillar. The ability to include laser dyes in high concentrations in a robust host framework with regulation of intermolecular association between the dye molecules may lead to new solid-state lasing materials that overcome some of the barriers encountered for dyes embedded as dilute solutes in amorphous solid-state matrices such as polymers, zeolites, and sol-gel glasses.

UR - http://www.scopus.com/inward/record.url?scp=68949136923&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=68949136923&partnerID=8YFLogxK

U2 - 10.1021/cg900578u

DO - 10.1021/cg900578u

M3 - Article

VL - 9

SP - 3803

EP - 3815

JO - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

IS - 8

ER -