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2D conjugated polyphthalocyanines can be obtained as two distinctly different types of material with specific molecular structures and different morphological properties. It was believed that the temperature is the key factor affecting the chemical reaction, but we show that even at the optimal temperature (420{\deg}C), the reaction on vapor/solid interface and liquid/solid interface yields different products: while the former is well-polymerized and ordered, the latter is amorphous and cross-linked with the typical conjugation scale of single PC ring. IR spectroscopy is most sensitive tool for identifying the molecular structure, providing the information on polymerization degree, structural uniformity and content of terminal groups. We show that, unlike the ordered PPCs, the cross-linked product can be reproducibly obtained as continuous conductive material.

We propose an experimental approach, by which thin films of copper polyphthalocyanine (CuPPC) can be directly synthesized in a chemical vapor deposition (CVD) set-up at mild temperature (420 {\deg}C). High polymerization degree and high crystallinity of the films was confirmed by TEM, FTIR and UV-VIS studies; the stacking structure of CuPPC layers was determined, inter-layer spacing was estimated from XRD and TEM electron-diffraction. Quantum-chemical study performed providing support for experimental structure determination and yielding information on the electronic structure., Comment: 6 pages, 11 figures