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Three new manganese(II) complexes, {[Mn(PTP)] 2 [Mn(PTP)(H 2 O)]}(BTA) 2 ·2H 2 O ( 1 ), [Mn(PTP)(ODA)] 2  ( 2 ), and [Mn(FTP)(ODA)] 2 ·H 2 O ( 3 ), were synthesized by the reactions of manganese acetate and polycarboxylic acid in the presence of  N -heterocyclic ligands (where PTP=4′-phenyl-2,2′:6′,2″-terpyridine, H 3 BTA=benzene-1,3,5-tricarboxylic acid, H 2 ODA=4,4′-oxydibenzoic acid, FTP=4′-(furan-2-yl)-2,2′:6′,2″-terpyridine). In complex  1 , each BTA ligand serves as a  μ  3 -bridge to link three Mn(II) centers, whereas each Mn(II) center is coordinated by two BTA ligands. This connection mode results in a grid sheet. Complexes  2  and  3  have very similar molecular structures with Mn(II) centers connected by ODA ligands to result in ring-like arrays. We investigated the third-order nonlinear optical (NLO) properties of the three complexes by single beam Z-scan techniques. Complexes  1 – 3  exhibit strong third-order NLO reverse saturable absorption with NLO absorptive indices  β =1.32×10 −6 , 3.01×10 −6 , and 9.42×10 −6  m W −1 , respectively. In addition, complex  1  shows all excellent self-focusing effect with an NLO refractive index of  γ =1.25×10 −12  m 2  W −1 . The third-order NLO susceptibility  χ  (3)  of the three complexes were calculated as 47.55×10 −8 , 4.85×10 −8 , and 15.16×10 −8  esu, respectively.

Crystal structures and third-order optical properties of three manganese(II) complexes constructed from N -heterocyclic and polycarboxylate ligands