Porous silver(I) organometallic coordination polymer of triptycene, and the guest desorption and absorption Ming Wen a , Megumu Munakata a, *, Yusaku Suenaga a , Takayoshi Kuroda-Sowa a , Masahiko Maekawa b a Department of Chemistry, Kinki University, Kowakae 3-4-1, Higashi-Osaka, Osaka 577-8502, Japan b Research Institute for Science and Technology, Kinki University, Kowakae, Higashi-Osaka, Osaka 577-8502, Japan Received 2 November 2001; accepted 1 February 2002 Abstract On the basis study of porous silver(I) complex of triptycene (tpty), [Ag 3 (tpty) 3 (ClO4) 3 ](toluene) 2 (1), its toluene desorbed complex (2) and absorbed complex (3) have been synthesized and confirmed by 1 H NMR spectra and X-ray powder diffraction. In complex 1, a 3D architecture with triptycene exhibits an unprecedented m /h 2  /h 2 or m  /h 2  /h 2  /h 1 coordination mode depending on the steric requirements of the network. The desorption and absorption of guest molecules occur in this complex accompanying the structure change. The potential study of these complexes for the rational control and synthesis of porous organometallic coordination network is discussed. # 2002 Elsevier Science B.V. All rights reserved. Keywords: Porous silver(I) complexes; Desorption and absorption; Organometallic complexes; Triptycene 1. Introduction The use of organic molecule and metal ions to control the self-assembly porous coordination polymers has been one of the most recent areas of the subject to develop. It is yielding new generations of open supra- molecular architectures [1,2]. Recent attention has focused on the formation of species with internal ca vities [3]. This is not only because of their intriguing structural diversity, but also because of their potential for applica- tions in molecular adsorptions, ion exchange and heterogeneous catalysis [4  /9]. Within these materials, diverse coordination geometries of building blocks give the pores possessing sizes and shapes of a variety yet unobserved in other crystalline porous solids such as zeolites and molecular sieves. Recently the metal /ligand coordination interactions are utilized in the directed assembly of a wide variety of 2-D and 3-D extended porous metal complex networks [6,8  /13] exhibiting unusual ion exchange [6,8], neutral guest exchange [10c] and selective adsorptive [10b] behavior. Within these networks two aspects, the preparation of large pores within the assembled struc- ture and integrity of the synthesized framework in the absence of guest inclusion, effect on many potentially important and interesting properties. In order to con- struct unusual porous architectures having novel incor- poration properties, many sophistication and diversity of ligand reactions and metal coordination chemistry are performed. Although the number of porous coordination poly- mers with new structural aspects have been reported so far, there is few porous coordination polymers con- structed by h 2 and h 1 -coordination modes of aromatic compounds to metal ions which reversibly incorporate guest molecules. We are currently engaged in a detailed study [14] of the coordination chemistry of a series of polyheteroaryl-substituted arenes tpty, which consist of various heterocyclic rings attached via silver(I) ions and anions. Such organometallic compounds are noted as a new type of porous coordination polymers. We have already reported [14] the synthesis and structure of porous silver(I) complex with triptycene (tpty), [Ag 3 (tp- * Corresponding author. Tel.:  /81-6-6730 5880x4119; fax:  /81-6- 6723 2721 E-mail address: munakata@chem.kindai.ac.jp (M. Munakata). Inorganica Chimica Acta 340 (2002) 8  /14 www.elsevier.com/locate/ica 0020-1693/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved. PII:S0020-1693(02)00875-7