The First Coordination Polymers Based on Octahedral Hexahydroxo Rhenium Cluster Complexes [Re 6 Q 8 (OH) 6 ] 4– (Q = S, Se) and Alkaline Earth Metal Cations

Seven novel octahedral cluster compounds [{Mg(H 2 O) 5 } 2 Re 6 S 8 (OH) 6 ] · 6H 2 O ( 1 ), [{Ca(H 2 O) 3 } 2 Re 6 S 8 (OH) 6 ] ( 2 ), [{Ca(H 2 O) 3 } 2 Re 6 Se 8 (OH) 6 ] ( 3 ), [{Sr 2 (H 2 O) 10 }Re 6 S 8 (OH) 6 ] · 6H 2 O ( 4 ), [{Sr 2 (H 2 O) 10 }Re 6 Se 8 (OH) 6 ] · 6H 2 O ( 5 ), [{Ba 2 (H 2 O) 8 }Re 6 S 8 (OH) 6 ] ( 6 ), and [{Ba 2 (H 2 O) 8 }Re 6 Se 8 (OH) 6 ] ( 7 ) were prepared by the direct reaction of K 4 [Re 6 S 8 (OH) 6 ] · 8H 2 O and K 4 [Re 6 Se 8 (OH) 6 ] · 8H 2 O with the cations of the elements of main group II. All compounds have been characterized by single crystal X‐ray diffraction. Compound 1 has a discrete molecular structure, compounds 4 and 5 have a one‐dimensional chain structure, and compounds 2 , 3 , 6 , and 7 crystallize in two different types of two‐dimensional layered structure. This sulfur containing series has been characterized by luminescent spectroscopy. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)