## 3 Experimental Section
### X-ray Crystallography  
The X-ray intensity data were collected with a MAR345 image plate (Norderstedt, Germany) using Mo-K\({}_{a}\) (\(\lambda\) = 0.71069 A) radiation. The crystal was chosen, mounted in inert oil and transferred quickly to the cold gas stream for flash cooling. Crystal data and data collection parameters are summarized hereafter. The unit cell parameters were refined using all the collected spots after the integration process. The data were not corrected for absorption (for **L**, **III**, **IV**), but the data collection mode partially takes the absorption phenomena into account. The structures were solved by direct methods with SHELXS [37]. The structure was refined by full-matrix least-squares on F\({}^{2}\) using SHELXL [37]. All non-hydrogen atoms were refined with anisotropic temperature factors. All hydrogen atoms were placed on calculated positions with temperature factors 1.2 times higher than their parent atoms (1.5 for methyl and OH hydrogens). The Fourier density map for **II** reveals a high residual peak next to the copper coordinated oxygen atom. Inspection of the native Patterson map reveals a large off origin peak (peak height \(>\) 50% orgin peak) positioned at 0.5 0 0.25, which is believed to indicate translational disorder. Applying the translation to the Cu atom situated on the 2-fold axis this gives a peak at 0.0000 0.7500 0.0901 or 0.5000 0.2500 0.5901 (+1/2 +1/2 +1/2) (given the **I** centering), which is also the position of the high residual peak in the Fourier map. The crystals (in total three full datasets were measured all giving the same outcome) have all some degree of non-crystallographic translational symmetry and thus consists of two domains which are translated by 1/2 in the \(z\)-direction. Figures were generated using the Mercury software [14]. **Crystal data for L:** C\({}_{8}\)H\({}_{6}\)N\({}_{8}\), \(M_{\rm r}\) = 178.18 g mol\({}^{-1}\), Monoclinic, space group \(C\)c, \(a\) = 3.7400(7), \(b\) = 21.081(4), \(c\) = 9.2000(18) A, \(\beta\) = 100.00(3)\({}^{\circ}\), \(V\) = 714.3(2) A\({}^{3}\), \(Z\) = 4, \(\rho\) = 1.657 g cm\({}^{-3}\), \(T\) = 293(2) K, \(\mu\)(Mo-K\(\alpha\)) = 0.122 mm\({}^{-1}\), reflections: 3630 collected, 1345 unique, \(R_{\rm int}\) = 0.0466, \(R_{\rm 1}\)(all) = 0.0399, \(wR_{\rm 2}\)(all) = 0.0958. **Crystal data for II:** C\({}_{8}\)H\({}_{16}\)CuF\({}_{12}\)N\({}_{16}\)OP\({}_{2}\), \(M_{\rm r}\) = 705.85 g mol\({}^{-1}\), tetragonal, space group \(I4_{1}/a\), \(a\) = \(b\) = 10.7557(1), \(c\) = 40.574(1) A, \(V\) = 4693.8(1) A\({}^{3}\), \(Z\) = 8, \(\rho\) = 1.998 g cm\({}^{-3}\), \(T\) = 100(2) K, \(\mu\)(Mo-K\(\alpha\)) = 1.204 mm\({}^{-1}\), reflections: 23,890 collected, 2243 unique, \(R_{\rm int}\) = 0.046, \(R_{\rm 1}\)(all) = 0.0758, \(wR_{\rm 2}\)(all) = 0.201. **Crystal data for III:** C\({}_{4}\)H\({}_{10}\)Cl\({}_{2}\)CuN\({}_{8}\)O, \(M_{\rm r}\) = 320.65 g mol\({}^{-1}\), monoclinic, space group \(P2_{1}/a\), \(a\) = 7.303(3), \(b\) = 13.838(5), \(c\) = 11.019(4) A, \(\beta\) = 101.67(2)\({}^{\circ}\), \(V\) = 1090.6(7) A\({}^{3}\), \(Z\) = 4, \(\rho\) = 1.953 g cm\({}^{-3}\), \(T\) = 101(2) K, \(\mu\)(Mo-K\(\alpha\)) = 2.486 mm\({}^{-1}\), reflections: 28,160 collected, 2225 unique, \(R_{\rm int}\) = 0.055, \(R_{\rm 1}\)(all) = 0.0316, \(wR_{\rm 2}\)(all) = 0.0915. **Crystal data for IV:** C\({}_{8}\)H\({}_{22}\)Cl\({}_{2}\)Cu\({}_{2}\)F\({}_{6}\)N\({}_{16}\)O\({}_{3}\)Si, \(M_{\rm r}\) = 730.51 g mol\({}^{-1}\), triclinic, space group \(P\)-1, \(a\) = 7.210(3), \(b\) = 11.673(4), \(c\) = 15.271(5) A, \(a\) = 70.35(2), \(\beta\) = 82.16(2), \(\gamma\) = 79.55(2)\({}^{\circ}\), \(V\) = 1186.4(8) A\({}^{3}\), \(Z\) = 2, \(\rho\) = 2.045 g cm\({}^{-3}\), \(T\) = 105(2) K, \(\mu\)(Mo-K\(\alpha\)) = 2.167 mm\({}^{-1}\), reflections: 19,683 collected, 4296 unique, \(R_{\rm int}\) = 0.066, \(R_{\rm 1}\)(all) = 0.0504, \(wR_{\rm 2}\)(all) = 0.1124. CCDC 902803 (**L**), 902805 (**II**), 902804 (**III**) and 902806 (**IV**) contain the supplementary crystallographic data.