Luminescent coordination polymers based on Ca2+ and octahedral cluster anions [{M6Cli8}Cla6]2− (M = Mo, W): synthesis and thermal stability studies

Luminescent coordination polymers (CPs) based on inexpensive stable precursors are attractive materials for applications. Here we report the synthesis and evaluation of the stability and photophysical characteristics of the first examples of phosphorescent CPs based on octahedral molybdenum and tungsten cluster anions. In particular, 1D CP trans-[{Ca(OPPh3)4}{{M6Cli8}Cla6}]∞ (M = Mo, W) can be obtained either directly at increased temperature or via intermediate phases [cis-Ca(OPPh3)4(H2O)2][{M6Cli8}Cla6]·2CH3CN that are stable at room-temperature, but convert to the titled CPs at temperatures above 100 °C.