The concept of rational design of micro-and mesoporous and other functional materials has attracted much attention because of the potential of these materials in various applications, such as molecular magnets, nonlinear optical devices, catalysts, molecular sieves, and sensors. [1] The construction of coordination networks possessing zeolite-or claylike structures offers great challenges and opportunities in terms of controlling their shape and size for selective adsorption. Much of the work has so far been focused on coordination polymers containing transition metal (Groups 8 to 10) and post-transition metal (Groups 11 and 12) elements including Fe, Co, Ni, Cu, Ag, Zn, Cd, and Hg. Rare-earth metal compounds have seldom been investigated. [2] To date, no systematic investigation across the lanthanide series with a single ligand has been carried out. Due to their high coordination number and special magnetic and fluorescence properties, the lanthanide series is likely to provide new materials that possess specific properties and desired features. In this communication, we report the hydrothermal synthesis, structures, and properties of six novel lanthanide coordination polymers and the investigation of the effects of lanthanide contraction and solution pH on the crystal structures of these compounds.Hydrothermal synthesis [3] is an effective and promising method for growing crystals of numerous inorganic compounds. Recently, we and others have successfully grown single crystals of a variety of transition metal coordination polymers using this approach. [4, 5] Our exploratory studies also show that the hydrothermal environment is suitable for preparation of lanthanide compounds.In this work, we have chosen a single, multifunctional ligand, 3,5-pyrazoledicarboxylic acid (H 3 pdc, 1), based on the following considerations: a) it has multiple coordination sites that allow structures of higher dimensions; b) it has an asymmetric geometry that may lead to acentric crystal structures; and c) it has abstractable protons that allow various, acidity-dependant coordination modes. In general, the lanthanide series can be divided into three groups according to their masses: the lighter La ± Pm (Group 1), the intermediate Sm ± Dy (Group 2), and the heavier Ho ± Lu (Group 3). Representative metals from each Group were selected and investigated.In a typical reaction 0.25 mmol of rare-earth metal(iii) nitrate and 0.25 mmol of 1 in 10 mL H 2 O was used. The mixture was placed into a 23 mL acid-digestion bomb lined with Teflon and heated at 150 8C for 3 days. Reactions with Group 1 lanthanide nitrates Ln(NO 3 ) 3 (Ln La, Ce) generated [Ln 2 (Hpdc) 3 (H 2 O) 4 ]´2 H 2 O, Ln La (2), Ln Ce (3). Group 2 nitrate Eu(NO 3 ) 3 produced [Eu 2 (Hpdc) 3 (H 2 O) 6 ] (4) and a minor product [Eu 2 (Hpdc) 3 (H 2 O) 4 ]´2 H 2 O that is isostructural to 2 and 3, while Group 3 nitrates Ln(NO 3 ) 3 (Ln Er, Lu) yielded [Er 2 (Hpdc) 3 (H 2 O) 6 ] (5), and [Ln(Hpdc)(H 2 pdc)(H 2 O) 2 ], Ln Er (6), Ln Lu (7).Single-phase polycrystalline samples of bo...