Hydrothermal crystallization of porphyrin-containing layer silicates

Porphyrins and metalloporphyrins have been demonstrated as organic templates in the hydrothermal crystallization of layered silicate smectite clays. Two water-soluble free-base porphyrins, tetrakis(N-methyl-4-pyridiniumyl)porphyrin (TMPyP) and tetrakis(N,N,N-trimethyl-4-aniliniumyl)porphyrin (TAP),...

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Bibliographic Details
Published in:Inorganic chemistry 1991-02, Vol.30 (4), p.794-799
Main Authors: Carrado, Kathleen A, Thiyagarajan, P, Winans, R. E, Botto, R. E
Format: Article
Language:English
Subjects:
400201 - Chemical & Physicochemical Properties
CARBOXYLIC ACIDS
CATALYTIC EFFECTS
Chemistry
CLAYS
COHERENT SCATTERING
Coordination compounds
CRYSTAL STRUCTURE
DATA
DIFFRACTION
Exact sciences and technology
EXPERIMENTAL DATA
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
Inorganic chemistry and origins of life
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
LAYERS
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PORPHYRINS
Preparations and properties
SCATTERING
X-RAY DIFFRACTION
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Summary:Porphyrins and metalloporphyrins have been demonstrated as organic templates in the hydrothermal crystallization of layered silicate smectite clays. Two water-soluble free-base porphyrins, tetrakis(N-methyl-4-pyridiniumyl)porphyrin (TMPyP) and tetrakis(N,N,N-trimethyl-4-aniliniumyl)porphyrin (TAP), along with metallo derivatives like Fe{sup III}TAP, were utilized as their chloride salts. Aqueous gels consisting of a 0.0166:0.20:1.00:1.52 porphyrin:LiF:Mg(OH){sub 2}:SiO{sub 2} molar ratio heated at reflux temperature crystallized synthetic porphyrin-containing hectorite clays in just 2 days. Results of x-ray powder diffraction indicated that the organic macrocycles are intercalated parallel between the clay layers. Microanalysis data and visible diffuse reflectance (DR) absorption spectra reveal that the porphyrin is incorporated intact. XRD and DR spectra also reveal that the free-base forms of the porphyrins dominate in hydrothermal crystallization products, while in ion-exchanged products the dication forms predominate. Small-angle neutron scattering (SANS) was used to follow the crystallization of these systems and to analyze interactions that exist when porphyrin is reacted with silica sol and magnesium hydroxide alone. Guinier analysis of the scattering curves yields structural information about the growth process of the clay system. Random network structures are observed for the porphyrin-silica system.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic00004a034