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

Polymer / Absorption band /cm-1 / Assignment / Functional group
1 / 3428 / asNH2 / NH2
3351 / NH2 / NH2
3240 / O-H / O-HO hydrogen
3038, 2964, 2871 / Ar-H / p-NH2C6H4COO
1651 / as(COO-) / COO
1493 / s(COO-) / COO
1592 / δN-H / NH2
1580, 1498, 1431 / C=C / p-NH2C6H4COO
1352 / C-N / p-NH2C6H4COO
1386 / ΔC-H / CH3
1183 / C-O / -COOH
795 / δAr-H / p-NH2C6H4COO
505 / Sm-N / Sm-N
397, 301 / Sm-O / Sm-O
2 / 3428 / asNH2 / NH2
3351 / NH2 / NH2
3242 / O-H / O-HO hydrogen
3034, 2971, 2863 / Ar-H / p-NH2C6H4COO
1651 / as(COO-) / COO
1402 / s(COO-) / COO
1592 / δN-H / NH2
1582, 1492, 1431 / C=C / p-NH2C6H4COO
1328 / C-N / p-NH2C6H4COO
1374 / ΔC-H / CH3
1182 / C-O / -COOH
794 / δAr-H / p-NH2C6H4COO
505 / Tb-N / Tb-N
396, 361 / Tb-O / Tb-O
3 / 3413 / asNH2 / NH2
3347 / NH2 / NH2
3235 / O-H / O-HO hydrogen
3040, 2930 / Ar-H / p-NH2C6H4COO
1662 / as(COO-) / COO
1502 / s(COO-) / COO
1606 / δN-H / NH2
1579, 1419,1396 / C=C / p-NH2C6H4COO
1354 / C-N / p-NH2C6H4COO
1386 / ΔC-H / CH3
1182 / C-O / -COOH
788 / δAr-H / p-NH2C6H4COO
510 / Pr-N / Pr-N
404, 387 / Pr-O / Pr-O
4 / 3365 / νO-H / H2O
3227, 2929 / νAr-H / 2, 5-dcp
1604, 1588 / as(COO-) / 2, 5-dcp
1459, 1397 / s(COO-) / 2, 5-dcp
1200-1000 / C–C / 2, 5-dcp
766 / δAr-H / p-NH2C6H4COO
519 / νPr–N / Pr–N
363 / νPr–O / Pr–O

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