Kazan Department of Joint Supercomputer Center of Russian Academy of Sciences-Branch of Federal Scientific Center "Scientific Research Institute for System Analysis of the RAS", Lobachevskii Street 2/31, 420111 Kazan, Russia.
Department of Analytical Chemistry, Certification and Quality Management, Kazan National Research Technological University, K. Marx Street 68, 420015 Kazan, Russia.
Int J Mol Sci. 2024 Jun 24;25(13):6897. doi: 10.3390/ijms25136897.
Using quantum chemical calculation data obtained by the DFT method with the B3PW91/TZVP and M062X/def2TZVP theory levels, the possibility of the existence of four Be(II) coordination compounds, each of which contains in the inner coordination sphere and the double deprotonated forms of subporphyrazine (H), mono[benzo]subporphyrazine (H), di[benzo]subporphyrazine (H), and tri[benzo]subporphyrazine (subphthalocyanine) (H) with a ratio Be(II) ion/ligand = 1:1, were examined Selected geometric parameters of the molecular structures of these (666)macrotricyclic complexes with closed contours are given; it was noted that BeN3 chelate nodes have a trigonal-pyramidal structure and exhibit a very significant (almost 30°) deviation from coplanarity; however, all three 6-membered metal-chelate and three 5-membered non-chelate rings in each of these compounds are practically planar and deviate from coplanarity by no more than 2.5°. The bond angles between two nitrogen atoms and a Be atom are equal to 60° (in the [Be] and [Be]) or less by no more than 0.5° (in the [Be] and [Be]). The presence of annulated benzo groups has little effect on the parameters of the molecular structures of these complexes. Good agreement between the structural data obtained using the above two versions of the DFT method was noticed. NBO analysis data for these complexes are presented; it was noted that, according to both DFT methods used, the ground state of the each of complexes under study is a spin singlet. Standard thermodynamic parameters of formation (standard enthalpy Δ, entropy , and Gibbs free energy Δ) for the above-mentioned macrocyclic compounds were calculated.
利用 DFT 方法，以 B3PW91/TZVP 和 M062X/def2TZVP 理论水平，获得了量子化学计算数据，研究了四种 Be(II)配位化合物的存在可能性，每个配位化合物的内配位球中都含有双去质子化的亚卟啉（H）、单[苯]亚卟啉（H）、二[苯]亚卟啉（H）和三[苯]亚卟啉（subphthalocyanine）（H），其比例为 Be(II)离子/配体=1:1。本文给出了这些具有封闭轮廓的（666）大环络合物分子结构的选定几何参数；注意到，BeN3 螯合节点具有三角双锥结构，与共面性的偏差非常显著（几乎 30°）；然而，在这些化合物中的每个化合物中，三个六元金属螯合环和三个五元非螯合环实际上都是平面的，与共面性的偏差不超过 2.5°。两个氮原子和一个 Be 原子之间的键角等于 60°（在[Be]和[Be]中）或不超过 0.5°（在[Be]和[Be]中）。稠合的苯基团的存在对这些配合物的分子结构参数影响不大。注意到，使用上述两种 DFT 方法得到的结构数据之间具有良好的一致性。本文还介绍了这些配合物的 NBO 分析数据；注意到，根据所使用的两种 DFT 方法，研究中每个配合物的基态都是单重态。计算了上述大环化合物的形成标准热力学参数（标准焓Δ、熵 和吉布斯自由能Δ）。
