The particle shape, Dcore and Dh were determined for all SCO CP-dBCP nanocomposite particles by TEM and DLS, respectively. The particle shape and core diameters (Dcryo) in solution were further analyzed by cryo-TEM for the samples 1-5e. As the SCO CP in the dBCP core has the highest electron density it appears black in TEM and cryo-TEM, whereas the PS corona is visible in light grey in TEM and not visible in cryo-TEM due to a lack in electron density contrast with respect to the vitrified THF matrix. The 20 samples 1-4, a-e all show spherical nanocomposite particles in TEM measurements (Figure and Figures ). The average core diameter Dcore increases continuously with rising P4VP fraction from 14 nm ± 2 nm (1e) to 58 nm ± 4 nm (4e) (see Table and Figure ). Furthermore, the core diameter of the nanocomposite samples does not change significantly with an increased cycle count. It is also independent of the used bipy excess during the synthesis, as determined by comparison of samples d and e. Cryo-TEM measurements also reflect the growth in the core sizes with increasing P4VP content. In line with the TEM measurements, spherical particles were observed for the SCO CP-dBCP nanocomposite samples 1-4e, showing also slightly larger core diameters than the empty dBCPs. The hydrodynamic diameters Dh of the nanocomposite particles, analyzed by DLS, increased along the series from 113 nm ± 67 nm (1e) to 139 nm ± 36 nm (4e) (Table and Figures S11-S15). It is observed that the hydrodynamic diameter slightly increases with a higher cycle count, which may be an effect of the crystallization of the CP inside the dBCPs core. In addition, the hydrodynamic diameter of the SCO CP-dBCP nanocomposite particles is significantly larger than the empty dBCP micelles. For the empty micelles the P4VP chains build the core. Upon addition of the coordination polymer the inner core is now formed by the complex that is surrounded by the P4VP chains. This most likely leads to an increased density of the P4VP chains on the surfaces and by this an increased stretching of the PS polymer chains and, thus, a larger hydrodynamic diameter (see Figure and). This effect diminishes in the composite particles when going from SV-15 to SV-42 because of the shorter PS chains. ). Dcryo of both, the spherical nanocomposite particles and the worm-like structures, are also marginally larger than the spherical particle cores observed for the neat dBCP (71 nm ± 4 nm (SV-61) vs. 84 nm ± 10 nm (5e)), in line with the other samples discussed here (Table ). However, Dcore (micelle width) of those worm-like structures determined by TEM in sample 5e with 60 nm ± 8 nm remained nearly identical to the particle size of sample 4e (see Figure ). The formation of rods in samples 5b-e is also indicated in the DLS measurements by the shift of the apparent size distribution to increasing particles sizes and an accompanied broadening of the size distribution, which is caused by the movement of the anisotropic rods/worms in solution (Figure ). In Figure ) and dividing it by the total weight of the sample. As a result, the weight fraction of the insoluble part increases to 82% (Table ). This indicates that the fraction of less soluble or insoluble parts needs to be around 80 % or higher for the formation of rods or worm-like structures. a) MeOH replaced by 4,4'-bipyridine during the synthesis and therefore considered as a solvent which is removed after the reaction, leading to the factor 0.86; b) only 1 equivalent bipy is involved in the formation of the CP, the excess is regarded soluble.