Calixarene‐Supported Polynuclear Cobalt(II) Cluster Complexes Tuned by Substitution Groups of the Second Bridging Ligands

A wheel‐like dodecanuclear cobalt(II) cluster complex [Co 12 (TBSOC) 4 (5‐NH 2 ‐tz) 8 (CH 3 OH) 6 ] · 3H 2 O · 5CH 3 OH ( 1 , 5‐NH 2 ‐tzH = 5‐amino‐1 H ‐tetrazole) and an irregular rod‐like tetradecanuclear cobalt(II) cluster complex [Co 14 (OH) 2 (TBSOC) 4 (5‐ph‐tz) 10 (5‐ph‐tzH) 2 (CH 3 OH) 2 ] · 16 · 5H 2 O · 2CH 3 OH( 2 , 5‐ph‐tzH = 5‐phenyl‐1 H ‐tetrazole) were solvothermally synthesized by using p ‐ tert ‐butylsulfonylcalix[4]arene (H 4 TBSOC) and 5‐subst‐1 H ‐tetrazoles as ligands. Single‐crystal X‐ray diffraction analyses revealed that the 5‐substituent groups of the 1 H ‐tetrazole bridging ligands have asignificant influence on the structure of the polynuclear cobalt(II) cluster complexes: 1 shows a closed wheel‐like structure whereas 2 an open rod‐like structure. A magnetic investigation indicated that both complexes exhibit antiferromagnetic properties.