DOI: 10.1002/adfm.200700717 Synthesis of Microscale Raft-shaped Zinc(II)–Phenylalanine Complexes and Zinc(II)–Phenylalanine/Dye Hybrid Bundles with New Optical Properties** By Huai-Ping Cong and Shu-Hong Yu* 1. Introduction Recent research efforts have focused on the fabrication of organic functional nanomaterials because of their widespread applications in the fields of electrics, [1] optics, [2] and chemical sensors, [3] as well as the advantage of achieving flexible organic materials via organic molecular design. To a large extent, the excellent functionalities of organic materials depend on their size and shape; thus, it is necessary to pay careful attention to the control of their morphology and dimensionality. Although many organic nanomaterials with different shapes, including nanotubes, [4] nanowires, [5] nanorods, [6] and other nanostruc- tures, [7] have been synthesized based on the self-assembly of an organic molecule, the ability to tune the size and morphology of organic materials lags well behind their inorganic counter- parts and needs to be improved urgently. Therefore, it is still a challenge to develop advanced methods to fabricate organic materials with uniform sizes and novel microstructures. Amino acids are a very important class of materials in biolog- ical organisms. Thus, a variety of studies on amino acids have been carried out in different fields. Because of the intense inter- est in the relationship between their morphologies and proper- ties, research is being carried out on new methods for control- ling the size and shape of amino acid nanostructures. Lahav and co-workers [8] reported the unmodified crystallization of D,L-ala- nine from a supersaturated solution without additives; Cölfen and co-workers [9] fabricated the alignment of D,L-alanine nano- crystals by a polymer-controlled crystallization approach, and D,L-alanine hollow tubes and core/shell mesostructures by the addition of a polymer and salt. [10] At the same time, the role of transition metals in biology can not be neglected. Metallopro- teins make up a third of all structurally characterized proteins, where transition metals play a crucial role in the catalytic and structural properties of the proteins. [11] Furthermore, zinc is especially important among the transition metals in the struc- tural organization of proteins. [12] Therefore, controlling the growth of zinc–amino acid complexes with novel microstruc- tures and special functionalities is an interesting subject. While pure organic [13,14] and inorganic materials [15,16] have been investigated for a long time, much attention has been dedicated into bifunctional [17,18] and multifunctional materi- als [19,20] in the past few years because of the attractive proper- ties obtained by combining heterogeneous materials. These functional nanomaterials include inorganic/inorganic materials, such as hybrids, [21,22] core/shell nanocomposites, [23–25] and inor- ganic/organic hybrid materials. [26–31] In contrast, achievements obtained in the fabrication of organic/organic hybrid materials are surprisingly few. [32] Therefore, it is necessary for more at- tempts to combine these organic materials into hybrid nanoma- terials with improved properties and novel functionalities. Adv. Funct. Mater. 2008, 18, 195–202 © 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 195 – [*] Prof. S. H. Yu, H.-P. Cong Division of Nanomaterials and Chemistry Hefei National Laboratory for Physical Sciences at the Microscale School of Chemistry and Materials University of Science and Technology of China Hefei 230026 (P.R. China) E-mail: shyu@ustc.edu.cn [**] This work is supported by special funding from the Centurial Pro- gram of the Chinese Academy of Sciences, the National Science Foundation of China (NSFC) (Grant nos.: 50732006, 20325104, 20621061, 20671085, 50372065), the 973 project (2005CB623601), Anhui Development Fund for Talent Personnel and Anhui Education Committee (2006Z027, ZD2007004-1), the Scientific Research Foun- dation for the Returned Overseas Chinese Scholars, the Specialized Research Fund for the Doctoral Program (SRFDP) of Higher Educa- tion State Education Ministry, the Partner Program of the Chinese Academy of Sciences, and the Max Planck Society. Supporting Infor- mation is available online from Wiley InterScience or from the author. Novel raft-like zinc(II)–phenylalanine complexes and zinc(II)–phenylalanine/acid green 27 (AG27) hybrid radial bundles have been successfully synthesized by a simple refluxing reaction. The formation processes of the morphologies and the superstruc- tures of the hybrid bundles were proposed based on the time-dependent evolution process. The AG27 molecules act as both the inclusion compound and the controller of the morphologies and the superstructures of the final hybrid. The combination of the zinc(II)–phenylalanine complex and AG27 leads to distinct optical properties compared with the individual component ma- terials. This approach opens a new and effective way for the fabrication of amino acid/dye hybrid materials with unique optical properties and is expected to allow access to other organic/organic hybrid materials with structural specificity and functional novelty. FULL PAPER