Electronic Supplementary Material (ESI) for CrystEngComm. This journal is © The Royal Society of Chemistry 2020 Supporting Information Table S1. Analysis results of Continuous Shape Measure (CSM) for Ln1 in cpdc-Ln CSM parameters * Ln1 JSD-8 BTPR-8 JBTPR-8 JETBPY- JGBF-8 TDD-8 SAPR- CU-8 HBPY- geometry 8 8 8 Eu1 9.453 6.003 6.644 27.526 20.710 5.891 5.282 13.610 20.003 Tb1 9.481 5.931 6.679 27.383 20.647 5.837 5.256 13.577 20.001 SAPR-8 Dy1 9.321 5.975 6.534 26.808 20.412 5.841 5.179 13.514 20.023 * HBPY-8→ Hexagonal bipyramid (D6h symmetry) CU-8→ Cube (Oh symmetry) SAPR-8→ Square antiprism (D4d symmetry) TDD-8→ Triangular dodecahedron (D2d symmetry) JGBF-8→ Johnson - Gyrobifastigium (J26) (D2d symmetry) JETBPY-8→ Johnson - Elongated triangular bipyramid (J14) (D3h symmetry) JBTP-8→ Johnson - Biaugmented trigonal prism (J50) (C2v symmetry) BTPR-8→ Biaugmented trigonal prism (C2v symmetry) JSD-8→ Snub disphenoid (J84) (D2d symmetry) Table S2. Analysis results of Continuous Shape Measure (CSM) for Ln2 in cpdc- Ln CSM parameters * Ln2 JTDIC- TCTPR- JTCTPR- CSAPR- JCSAPR- CCU-9 JCCU-9 JTC-9 HBPY- geometry 9 9 9 9 9 9 Eu2 17.653 18.362 17.250 17.382 15.938 10.071 8.314 18.552 18.091 Tb2 18.055 18.685 17.314 17.693 16.135 10.357 8.469 18.937 18.196 JCCU-9 Dy2 18.602 18.713 17.193 17.730 16.131 10.403 8.465 19.327 18.014 * HBPY-9→ Heptagonal bipyramid (D7h symmetry) JTC-9→ Triangular cupola (J3) = trivacant cuboctahedron (C3v symmetry) JCCU-9→ Capped cube (Elongated square pyramid, J8) (C4v symmetry) CCU-9→ Capped cube (C4v symmetry) JCSAPR-9→ Capped sq. antiprism (Gyroelongated square pyramid J10) (C4v symmetry) CSAPR-9→ Capped square antiprism (C4v symmetry) JTCTPR-9→ Tricapped trigonal prism (J51) (D3h symmetry) TCTPR-9→ Tricapped trigonal prism (D3h symmetry) JTDIC-9→ Tridiminished icosahedron (J63) (C3v symmetry) 1 Table S3. Analysis results of Continuous Shape Measure (CSM) for Ln1 in cpdc-bc-Ln CSM parameters * Ln1 geometry MFF-9 HH-9 JTDIC-9 TCTPR-9 JTCTPR-9 CSAPR-9 JCSAPR-9 CCU-9 JCCU-9 Eu1 19.812 19.563 22.594 20.464 13.937 20.384 19.375 21.988 20.093 Tb1 19.827 19.644 22.713 20.443 13.925 20.358 19.337 22.170 20.314 JTCTPR-9 Dy1 19.872 19.630 22.671 20.528 13.950 20.420 19.385 22.170 20.283 * JCCU-9→ Capped cube (Elongated square pyramid, J8) (C4v symmetry) CCU-9→ Capped cube (C4v symmetry) JCSAPR-9→ Capped sq. antiprism (Gyroelongated square pyramid J10) (C4v symmetry) CSAPR-9→ Capped square antiprism (C4v symmetry) JTCTPR-9→ Tricapped trigonal prism (J51) (D3h symmetry) TCTPR-9→ Tricapped trigonal prism (D3h symmetry) JTDIC-9→ Tridiminished icosahedron (J63) (C3v symmetry) HH-9→ Hula-hoop (C2v symmetry) MFF-9→ Muffin (Cs symmetry) Figure S1. (a) The coordination environment for Eu1 in cpdc-Eu; (b) The distorted square antiprismatic geometry for Eu1 in cpdc-Eu; (c) The coordination environment for Eu2 in cpdc-Eu;(d) The distorted elongated square pyramid geometry for Eu2 in cpdc-Eu. symmetry codes: A (x, 1.5-y, z), B (1-x, 1-y, -z), C (1-x, 0.5+y, -z), D (x, 0.5-y, z), E (2-x, -0.5+y, 1-z), F (2-x, 1-y, 1-z),G (1-x, -0.5+y, -z), H (x, -1+y, z), I (x, 1+y, z). 2 Figure S2. 2D double chain layer structure involving hydrogen bonds in cpdc-Eu. The green dotted lines denote the distance of D∙∙·A involved in the hydrogen bonding. Figure S3. (a) The coordination environment for Eu1 in cpdc-bc-Eu; (b) The distorted tricapped trigonal prismatic geometry for Eu1 in cpdc-bc-Eu. Symmetry codes: A (1-x, -0.5+y, 0.5- z), B (1-x, 0.5+y, 0.5-z). 3 Figure S4. The experimental and simulated PXRD patterns for cpdc-Eu. The top is the experimental pattern, and the bottom is the simulated one. Figure S5. The experimental and simulated PXRD patterns for cpdc-Tb. The top is the experimental pattern, and the bottom is the simulated one. 4 Figure S6. The experimental and simulated PXRD patterns for cpdc-Dy. The top is the experimental pattern, and the bottom is the simulated one. Figure S7. The experimental and simulated PXRD patterns for cpdc-bc-Eu. The top is the experimental pattern, and the bottom is the simulated one. 5 Figure S8. The experimental and simulated PXRD patterns for cpdc-bc-Tb. The top is the experimental pattern, and the bottom is the simulated one. 6 Figure S9. The experimental and simulated PXRD patterns for cpdc-bc-Dy. The top is the experimental pattern, and the bottom is the simulated one. 7 Figure S10. The measurement details of solid state fluorescence quantum yield for cpdc-Eu (top, λex=394 nm) and cpdc-Tb (down, λex=368 nm) under direct excitation condition. 8 Figure S11. The measurement details of solid state fluorescence quantum yield for cpdc-bc-Eu under direct excitation (top, λex=394 nm) and sensitized excitation conditions (down, λex=287 nm) 9 Figure S12. The measurement details of solid state fluorescence quantum yield for cpdc-bc-Tb under direct excitation (top, λex=368 nm ) and sensitized excitation conditions (down, λex=287 nm) 10 Figure S13. Simulation of the magnified emission spectrum of the 4F9/2 6H15/2 transition of cpdc-bc-Dy at room temperature through a convolution of Gaussian lines corresponding to eight 6H15/2 multiplets (R2=0.992908). Figure S14 A linear plot for the exponential logarithm of the magnetization relaxation time versus the reciprocal of the peak temperature 11 Figure S15 Temperature dependence of the in-phase (χ′) (top) and out-of-phase (χ″) (bottom) ac susceptibility signals at different frequencies with Hdc = 0 Oe (left) and Hdc = 2000 Oe (right) for cpdc- Dy. Figure S16. FT-IR spectra for cpdc-Eu 12 Figure S17. FT-IR spectra for cpdc-Tb Figure S18. FT-IR spectra for cpdc-Dy 13 Figure S19. FT-IR spectra for cpdc-bc-Eu Figure S20. FT-IR spectra for cpdc-bc-Tb 14 Figure S21. FT-IR spectra for cpdc-bc-Dy 15.