Intercalation compounds involving inorganic layered structures

Abstract

Two-dimensional inorganic networks can shown intracrystalline reactivity, i.e., simple ions, large species as Keggin ions, organic species, coordination compounds or organometallics can be incorporated in the interlayer region. The host-guest interaction usually causes changes in their chemical, catalytic, electronic and optical properties. The isolation of materials with interesting properties and making use of soft chemistry routes have given rise the possibility of industrial and technological applications of these compounds. We have been using several synthetic approaches to intercalate porphyrins and phthalocyanines into inorganic materials: smectite clays, layered double hydroxides and layered niobates. The isolated materials have been characterized by elemental and thermal analysis, X-ray diffraction, surface area measurements, scanning electronic microscopy, electronic and resonance Raman spectroscopies and EPR. The degree of layer stacking and the charge density of the matrices as well their acid-base nature were considered in our studies on the interaction between the macrocycles and inorganic hosts.

Modes of tetra(4-pyridyl)porphyrinatomanganese(III) ion intercalation inside natural clays

“…Alternatively, a stack of octahedral layer can be sided by two tetrahedral stacks (in Montmorillonite). The surfaces of each layer involve OH groups, which allow inter-planar H-bond attractions that hold the total structure intact [ 19 ]. Depending on the combinations of the silicon and aluminum ions, the clay frameworks carry net zero or negative charges.…”

“…Tubular halloyasites have also been described for metalloporphyrin intercalation purposes [ 29 ]. Constantino et al reported the intercalation of metalloporphirins inside different types of inorganic solids, namely smectite clays, layered double hydroxides and layered niobates in their separate phases [ 19 ]. They showed that intercalation inside clays occurred horizontally, while in layered double hydroxides intercalation occurred perpendicularly.…”

New Hybrid Materials Based on the Water Soluble Zinc Phthalocyanines and V2O5·nH2O

“…[1][2][3][4][5] Слоистые материалы служат в качестве матриц для биологически и катали-тически активных молекул, таких как порфирины и фталоцианины, обладающих важнейшим фотофизиче-ским свойством генерации синглетного кислорода, что обусловливает их широкое применение в качестве фото-сенсибилизаторов для фотодиагностики и фототерапии злокачественных новообразований, активных компо-нентов сенсорных устройств, альтернативных матери-алов для солнечных батарей, гомогенных и гетерогенных катализаторов в процессах окислительной деструкции токсичных ароматических систем (фенолов) и демер-каптанизации углеводородных бензиновых фракций и нефтей. [6][7][8][9] Однако, фотосенсибилизирующая способ-ность фталоцианинов, особенно в водных растворах, снижается вследствие их ассоциации в агрегаты.…”

Studies of porphyrin zinc compounds intercalated into V2O5 xerogel

“…1 The interest in xerogel arose 25 years ago in the connection with the discovery of its semiconducting prop erties and the use of xerogels as antistatic coatings in photographic industry. 2 Different methods of synthesis of vanadium(V) pentoxide xerogel both from inorganic 3 and organic starting materials are known.…”