Hydrogen-bonded frameworks based on hetero-trimers and -tetramers of octahedral cluster unit [Ta6Cl12(CN)6]3− and Mn complexes

[Ta6Cl12(CN)6]3- and Mn complexes were facilely prepared and used to make hydrogen-bonded frameworks built of hetero-trimers and −tetramers of the cluster units via solution syntheses. [Display omitted] •Hexanuclear [Ta6Cl12(CN)6]4- and [Ta6Cl12(CN)6]3- were facilely prepared from Ta6Cl14⋅8H2O via solution syntheses.•A heterotetramer built of three Mn(III) complexes connected to an octahedral cluster unit in the meridional-mode is reported.•[Ta6Cl12(CN)6]4- is found to be oxidized more easily than [Nb6Cl12(CN)6]4-, in agreement with previous electrochemical measurement results. Octahedral tantalum chlorido-cyanido cluster units, [Ta6Cl12(CN)6]4- and [Ta6Cl12(CN)6]3-, were synthesized from Ta6Cl14⋅8H2O via solution syntheses, yielding [Me4N]4[Ta6Cl12(CN)6] (1) and [Na3(MeCN)2(H2O)4][Ta6Cl12(CN)6] (2). 1 and 2 reacted with two distinct [MnIII(SB)]+ complexes (SB: a Schiff-base ligand) to produce [Me4N]{[Mn(H2O)(salen)]2[Ta6Cl12(CN)6]} ·2H2O (3) (salen2-= bis(salicylidene)ethylenediamine) and [Mn(acen)(H2O)]3[Ta6Cl12(CN)6]· 4EtOH·2H2O (4) (acen2- = bis(acetylacetonato)ethylenediamine). Single-crystal X-ray diffraction (SCXRD) and PXRD analyses confirmed the structures of all compounds. 1 is an ionic compound built of [Me4N]+ and [Ta6Cl12(CN)6]4-. 2 exhibits a neutral three-dimensional (3D) Prussian-blue structure composed of trinuclear [Na3(MeCN)2(H2O)4]3+ and hexanuclear [Ta6Cl12(CN)6]3- interconnected by CN–. 3 features a 3D hydrogen-bonded framework comprising heterotrimers {[Mn(H2O)(salen)]2[Ta6Cl12(CN)6]}- balanced by [Me4N]+. 4 possesses a 1D hydrogen-bonded structure formed by neutral heterotetramers {[Mn(acen)(H2O)]3[Ta6Cl12 (CN)6]}. Their UV–Vis, IR, thermal behaviors are discussed.