A Series of Lanthanide-Germanate Oxo Clusters Decorated by 1,10-Phenanthroline Chromophores.

A series of lanthanide-germanate oxo clusters, [Ln8(phen)2Ge12(μ3-O)24T12(H2O)16]·2H2O [Ln = Dy (1a) and Er (1b); T = -CH2CH2COO- group; phen = 1,10-phenanthroline], [Ln8(phen)2Ge12(μ3-O)24T12(H2O)16]·2phen·16H2O [Ln = Sm (2a), Eu (2b), and Gd (2c)], and [Ho8(phen)2Ge12(μ3-O)24T12(H2O)14]·2phen·13H2O (3), have been hydrothermally synthesized from the reactions of bis(carboxyethylgermanium sesquioxide) and Ln2O3 with auxiliary phen chromophores. Compounds 1a and 1b consist of cage clusters [Ln8(phen)2Ge12(μ3-O)24T12(H2O)16] and free H2O molecules, where cage clusters are arranged in a CsCl type, while compounds 2a-2c consist of cage clusters [Ln8(phen)2Ge12(μ3-O)24T12(H2O)16], free phen, and free H2O molecules, where cage clusters are arranged in a NaCl type. Compound 3 consists of the one-dimensional neutral chain [Ho8(phen)2Ge12(μ3-O)24T12(H2O)14]n and free H2O molecules. These compounds provide the first examples of p-f heterometallic [Ge-O-Ln] oxo clusters decorated by phen chromophores. The photoluminescent and magnetic properties of all compounds have been investigated.