1. the Structural Figures of Polymers

SupplementaryMaterials

1. The structural figures of polymers

Fig.S1 The 3D hydrogen bond network of polymer 1

Fig.S2 Hydrogen bonds of polymer 3along c direction

Fig.S3 3D hydrogen bond network of polymer 3

Fig.S4 2D layer structure of polymer 4 in bc plane

(Lattice water molecules are omitted for clarity)

Fig.S5The linking mode of polymer 4 along a direction

Fig.S6 The 3D network of polymer 4 (Lattice water molecules are omitted for clarity)

2. The explanation for the structure of polymer 2

For polymer 2, the R1 and wR2 values are highbecause itscrystalqualityisnotgood. After structure refinement, the values of Q peaks around the Tb3+ ion are high, and the distances between the Tb3+ ion and Q are excluded from forming the reasonable bands, i. e., the assignments for the Q peaks are not unreasonable. However,incomparisonwiththecomplex1,complex 2 hasthesamecrystalsystemandspacegroup,similarcrystalcellstructure,the IR spectrum of polymer 2 is same as that of polymer 1 (Figs. S5, S6), meanwhile,itselementalanalysisresultsapproximateitspredictedmolecularformula. These prove further the validity of the structure for polymer 2.

3. The assignments for the IR spectra of polymers 14

The IR spectra of the four polymersare recorded in 200～4000 cm-1 region with pressed KBr and they present the characteristic bands of functional groups from ligands and the coordination bands from metal ions to ligands (Figs S5S8). Polymers 13 possess same ligands and analogical coordination modes except for the central metal ions, so their spectra are resemble. The assignments of the IR spectrum for polymers 14are listed in table S1.

In comparison with the IR spectra of corresponding ligands, the spectrum of polymer 1 shows the characteristic groups of ligands and the coordination characteristic between central ions and ligands (Fig. S5) as follows. The carboxy vibration of ligand (p-aminobenzoic acid) disappears at 1663cm-1, while the asymmetric stretching vibration (1651 cm-1) and symmetric stretching vibration (1493 cm-1) of carboxylate group (COO) appear which indicates that the carboxylate group takes part in coordination. In addition, the difference between the two vibrations is less than 200cm-1 which indicates that both of the two carboxylic oxygen atoms take part in coordination, this can be further proved by the Sm-O vibration at 397 cm-1. The results are according with the determination of the single-crystal X-ray diffraction. The vibration bands at 3428 cm-1 and 3351 cm-1 can be respectively assigned to symmetric stretching vibration and symmetric stretching vibration of amino (NH2), and the bending vibration of N-H(δN-H, 1592nm) indicates the existence of amino. In addition, the peaks at 1352cm-1 and 1386cm-1 is assigned to the stretching vibration of C-N and C-H, respectively, and the band at 505 cm-1 is assigned to the vibration of Sm-N which indicates that the DMF also coordinates to the Ln3+ ion.

The spectrum of polymer 4 exhibits the characteristic bands of pydine-2,5-dicarboxylic acid (Fig. S8). The asymmetric stretching vibrations of carboxylate group (COO) appear at 1604cm-1 and 1588cm-1, and the symmetric stretching vibrations appear at 1459cm-1 and 1397cm-1, while the differences between the two pairs of vibrations are less than 200cm-1 which indicates that both of the two carboxylic oxygen atoms take part in coordination. The band at 519 cm-1 is assigned to the vibration of Pr-N and the band at 363 cm-1 is assigned to the vibration of Pr-O. The broad band at 3365cm-1 should be attributed to the water molecules in the crystal. The assignments of IR spectra for polymers 1 and 4 are summarized in Table S1.

Table S1The assignments of theIR spectraforpolymers14

Fig.S5 IR spectrum of polymer 1 Fig.S6 IR spectrum of polymer 2

Fig.S7 IR spectrum of polymer 3 Fig.S8 IR spectrum of polymer 4

4. The excitation spectra of polymers 1-3

Fig.S9The excited spectrum of polymer 1 Fig.S10The excited spectrum of polymer 2

(λem = 600 nm) (λem = 544 nm)

Fig.S11The excited spectrum of polymer 3(λem = 407 nm)

S1