Supporting Information



Table S1. Crystallographic data for compound [(Cu(hfa)2)2(4-tpt)]n (1) determined by SR-PXRD.
                 Compound                                                 [(Cu(hfa)2)2(4-tpt)]n (1)
                 Empirical formula                                           C38H16F24N6O8Cu2
                 Formula weight                                                   1267.67
                 Measurement T (K)                                                 298(2)
                 Wavelength (Å)                                                   0.49587
                 System, space group                                        Monoclinic, P21 (4)
                 a (Å)                                                          10.5172(2)
                 b (Å)                                                          25.4118(4)
                 c (Å)                                                          10.0730(2)
                 α (°)                                                               90
                 β (°)                                                          112.974(1)
                 γ (°)                                                               90
                 Volume (Å3)                                                    2478.60(10)
                 Z                                                                    2
                 Dcalc (g cm-3)                                                    1.699
                 2θ range (°) collected (step)                            0.776 to 43.496 (0.006)
                 Rietveld refinement details:
                 Profile function                                               Pseudo-Voigt
                 2θ range (°) used for refinement                              1.800 to 30.000
                 Number of reflections                                              3029
                 Number of data points                                              4700
                 Parameters1                                                         250
                 Restraints                                                          265
                 Rwp                                                               0.0623
                 Rexp                                                              0.0035
                 χRietveld/ χPattern-Matching                                       1.56
                 1 Parameters:  233 atomic coordinates, zero, scale factor, 9 atomic displacements, 2 profile, 4
                 cell.
                 2 Restraints: 86 bond distances, 118 bond angles, 61 distances to a plane
Table S2. Crystallographic data for compound [(Cu(hfa)2)(4-tpt)]n (2) determined by single
crystal XRD.

                 Compound                                     [(Cu(hfa)2)(4-tpt)]n (2)
                 Empirical formula                              C28H14F12N6O5.5Cu
                 Formula weight                                        813.99
                 Measurement T (K)                                     100(2)
                 Wavelength (Å)                                       0.72932
                 System, space group                                  P 21 21 2
                 a (Å)                                               20.001(9)
                 b (Å)                                               26.390(3)
                 c (Å)                                               6.3800(3)
                 α (°)                                                   90
                 β (°)                                                   90
                 γ (°)                                                   90
                 Volume (Å3)                                        3367.6(16)
                 Z                                                        4
                 Dcalc (g cm-3)                                        1.606
                 µ (mm-1)                                              0.812
                 F(000)                                                1620.0
                 Crystal size (mm3)                             0.050x0.040x0.010
                 hkl ranges                               -26≤h≤26, -35≤k≤35, -8≤l≤8
                 2θ range (°)                                     1.311 to29.089
                 Reflections collected/unique/[Rint]       53652/8357/[Rint = 0.0418]
                 Completeness                                           100%
                 Refinement method                      Full matrix least-squares on |F|2
                 Data/restrains/parameters                         8357/0/ 475
                 Goodness of fit (GOF) on |F|2                         1.034
                 Final R indices [I>2σ(I)]                 R1 = 0.0660, wR2 = 0.1827
                 R indices (all data)                     R1 = 0.0689, wR2 = 0.1863
                 Extinction coefficient                             0.0029(10)
                 Largest. Diff. peak and hole (e Å-3)            2.898 and -0.697
FIGURE S1. Crystal structure of [(Cu(hfa)2)2(4-tpt)]n (1) displaying the detail of the coordination
sphere of the two independent Cu(II) atoms (Cu1a and Cu1b). Only the linked pyridine ring of
the 4-tpt ligand is shown. Hydrogen atoms are omitted for clarity.




FIGURE S2. Crystal structure of [(Cu(hfa)2)2(4-tpt)]n (1) showing the interaction between
pentacoordinated Cu(II) atoms and the triazine ring of a neighbor chain. Hydrogen atoms are
omitted for clarity.
FIGURE S3. Crystal structure of [(Cu(hfa)2)(4-tpt)]n (2) detailing the coordination sphere of the
Cu(II) atom. Only the linked pyridine ring of 4-tpt ligands is shown. Hydrogen atoms are
omitted for clarity.




FIGURE S4. Crystal structure of [(Cu(hfa)2)(4-tpt)]n (2) showing the interchain interactions
involving the non-coordinated pyridine ring and the triazine ring of an adjacent chain.
FIGURE S5. Void space analysis of [(Cu(hfa)2) (4-tpt)]n (2).




FIGURE S6. FTIR-ATR spectra of compounds [(Cu(hfa)2)2(4-tpt)]n (1) (down, black line) and
[(Cu(hfa)2)(4-tpt)]n (2) (up, red line).
FIGURE S7. PXRD patterns of [(Cu(hfa)2)(4-tpt)]n (2) obtained by phase transformation of (1):
(bottom, blue line) simulated from crystal structure data; (medium, black line) sample obtained
from treatment of (1) in EtOEt and after activation under vacuum; and (up, red line), for
comparison, sample obtained from the amorphous compound precipitated in CHCl3 and
recrystallized in EtOET after activation under vacuum.




FIGURE S8. TGA curves of [(Cu(hfa)2)2(4-tpt)]n (1) (black line) and [(Cu(hfa)2)(4-tpt)]n (2) (red
line).
FIGURE S9. Void space analysis of [(Cu(hfa)2)2(4-tpt)]n (1).




FIGURE S10. Calculated Isosteric heat of adsorption (Qst) at different surface coverages of CO2
on [(Cu(hfa)2)(4-tpt)]n (2).
FIGURE S11. Observed (red points), calculated (black line) and difference (blue line) PXRD
patterns for [(Cu(hfa)2)2(4-tpt)]n (1). Positions of the Bragg reflections are represented by
vertical green bars.