Review Molecular sieves as host materials for supramolecular organization Dominik Br€ uhwiler, Gion Calzaferri * Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3000 Bern 9, Switzerland Received 21 October 2003; received in revised form 8 March 2004; accepted 12 March 2004 Available online 18 May 2004 Abstract The use of zeolites and mesoporous silicas (M41S family) as host materials for the supramolecular organization of organic dye molecules, metal sulfide clusters, and transition metal complexes is reviewed. For dye–zeolite systems, different stages of organi- zationarediscussed,rangingfromthearrangementofthedyesinthezeolitechannelstothespecificadsorptionofmoleculesatthe channel entrances and finally to the coupling of the dye–zeolite crystals to an external device. The synthesis of metal sulfide nanoparticles in zeolites is illustrated by our studies of silver sulfide clusters in zeolite A. Starting from an activated Ag þ -loaded zeolite,thesynthesisexploitsthedefinedstructureofthezeoliteframeworktoachievecontrolledclustergrowthyieldingcomposites withuniqueluminescenceproperties.TheorganizationofguestspeciesinmesoporoussilicasoftheM41Sfamilyismostlyrelatedto the chemistry of the surface silanol groups. This aspect is discussed with particular emphasis on the functionalization with organic chromophores and the grafting of isolated transition metal centers through oxo-bridges. Ó 2004 Elsevier Inc. All rights reserved. Keywords: Zeolite; Mesoporous silica; Supramolecular organization; Inclusion of organic dye molecules and semiconductor clusters; Grafting of transition metal complexes Contents 1. Preface ................................................................................. 2 2. Supramolecular organization of organic dye molecules in zeolites........................................ 2 2.1. Introduction ......................................................................... 2 2.2. First stage of organization ............................................................... 3 2.2.1. Insertion and diffusion ........................................................... 3 2.2.2. Determination of loading levels ..................................................... 7 2.2.3. Orientation ................................................................... 7 2.2.4. Interaction between the dye molecules ................................................ 9 2.2.5. Interaction of the dye molecules with the zeolite ........................................ 10 2.3. Second stage of organization ............................................................ 11 2.4. Third stage of organization ............................................................. 12 2.4.1. Macroscopic ordering ........................................................... 12 2.4.2. Coupling to external devices ........................... ........................... 12 3. Supramolecular organization of metal sulfide particles in zeolites ....................................... 13 3.1. Introduction ........................................................................ 13 3.2. From silver ions to silver sulfide clusters .................................................... 14 3.2.1. Silver ions in zeolite A .......................................................... 14 3.2.2. Silver sulfide cluster growth ....................................................... 14 * Corresponding author. Fax: +41-31-6313994. E-mail addresses: dominik.bruehwiler@iac.unibe.ch (D. Br€ uhwiler), gion.calzaferri@iac.unibe.ch (G. Calzaferri). 1387-1811/$ - see front matter Ó 2004 Elsevier Inc. All rights reserved. doi:10.1016/j.micromeso.2004.03.027 www.elsevier.com/locate/micromeso Microporous and Mesoporous Materials 72 (2004) 1–23