In this study, Density Functional Theory and the Boltzmann transport equation are applied to calculate the semiclassical thermoelectric transport properties of phthalocyanine (PC) covalent organic frameworks with different central metals in the macrocycle MPc-COFs, (M = Co, Cu, and Zn), which have a slipped-AA stacking of 2D polymer sheets. The weakening of π-π stacking increased the role of in-plane intramolecular through-bond carrier transfer involving σ/π interactions, leading to significant anisotropy of transport coefficients in the studied compounds, which are also affected by the nature of the transition metals. The maximum values of thermopower for Co-Pc COF (770 μV/K) and Cu-Pc COF (− 423 μV/K) were found along the in-plane direction. However, for ZnPc-COF, the maximum positive value of the Seebeck coefficient (156 μV/K) was found along the stacking direction, while the maximum value of the thermopower along the in-plane direction was equal to − 315 μV/K. The electronic fitness function was calculated to estimate the thermoelectric performance of the studied compounds for both p- and n-type doping at 300 and 800 K. The maximum values of the electronic fitness function are observed for Cu-Pc and Zn-Pc COFs along the stacking direction at 800 K for both p- and n-type doping, while for p-doped Co-Pc COF the maximum value of this function was found along the in-plane direction.

在这项研究中，应用密度泛函理论和玻尔兹曼输运方程来计算大环MPc-COFs中具有不同中心金属的酞菁（PC）共价有机骨架的半经典热电输运性质，（M = Co，Cu和Zn） ，其中具有2D聚合物薄板的滑动AA堆叠。π-π堆积的削弱增加的作用在-平面涉及分子内通过键托架搬出σ /π相互作用，导致在所研究的化合物输送系数，其也受到过渡金属的性质显著各向异性。在-方向上发现了Co-Pc COF（770μV/ K）和Cu-Pc COF（− 423μV/ K）的最大值。平面方向。然而，对于的ZnPc-COF，塞贝克系数（156μV/ K）的最大正值被沿着堆叠方向发现，同时沿着热电动势的最大值在-平面方向等于- 315μV/ K。计算电子适应度函数以估算所研究化合物在300和800 K时对p型和n型掺杂的热电性能。观察到Cu-Pc和Zn-Pc COF沿电子适应度的最大值p型和n型掺杂在800 K时的堆叠方向，而p型掺杂的Co-Pc COF的最大值沿在-平面方向。