Four coordination clusters using fluorenyl and carbazyl phosphonates as ligands

Four polynuclear complexes, [Co sub(4)(FluPO sub(3)) sub(2)(FluPO sub(3)H) sub(2)(CH sub(3)CO sub(2)) sub( 2)(py) sub(6)(H sub(2)O ) sub(2)] (1), [Mn sub(5)O sub(3)(FluPO sub(3)) sub(2)(PhCO sub(2)) sub(5)(CH sub(3)OH)(phen) sub( 2)] (2), [Mn sub(5)O sub(3)(CarbPO sub(3)) sub(2)(PhCO sub(2)) sub(5)(CH sub(3)OH)(phen)d2 (3) and [Mn super(II) sub(4)Mn super(III) sub(6)O sub(2)(OH) sub(2)(CarbPO sub(3)) sub(8)(PhCO sub(2) sub(4)(py) sub(6)] (4) (FluPO sub(3)H sub(2) = (9-methyl-9H-fluoren-9-yl)phosphonic acid, CarbPO sub(3)H sub(2) = N-carbazolylmethylphosphonic acid), were synthesized and characterized. In compound 1, the cobalt centers are bridged by phosphonate ligands into a circle. Both the cores of complexes 2 and 3 feature three mu sub(3)-O and two capping FluPO sub(3) super(2-) or CarbPO sub(3) super(2-) groups bridging five Mn super(III) atoms to form a basket-like cage structure. Complex 4 contains divalent and trivalent ions and has a butterfly-like [Mn super(II) sub(4)Mn super(III) sub(6)O sub(2)(OH) sub(2)(CarbPO sub(3)) sub(4)] super(12 +) core with four phosphonate ligands in the body position and five Mn atoms on each wing side. Magnetic susceptibility measurements reveal the existence of antiferromagnetic interactions in 1, 2.4CH sub(3)CN.2H sub(2)O, 3.PhCO sub(2)H.6CH sub(3)CN.2H sub(2)O and 4.py.8H sub(2)O. Fitting the experimental data led to the following parameters: J sub(1) = -10.1 cm super(-1), J sub(2) = -18.0 cm super(-1), J sub(3) = -8.0 cm super(-1), J sub(4) = -5.9 cm super(-1), J sub(5) = -2.8 cm super(-1), g= 2.0 for 2.4CH sub(3)CN.2H sub(2)O, and J sub(1) = -7.4 cm super(-1), J sub(2) = -22.8 cm super(-1), J sub(3) = -6.9 cm super(-1), J sub(4) = -4.8 cm super(-1), J sub(5) = -0.3 cm super(-1), g= 2.0 for 3.PhCO sub(2)H.6CH sub(3)CN.2H sub(2)O.