Departamento de Nanoestructuras, Superficies, Recubrimientos y Astrofísica Molecular , Instituto de Ciencia de Materiales de Madrid (ICMM-CSIC) , 28049 Madrid , Spain.
Departamento de Química Inorgánica, Instituto de Ciencia Molecular (ICMol) , Universidad de Valencia , Parque Científico, Catedrático José Beltrán, 2 , 46980 Paterna Valencia , Spain.
Inorg Chem. 2018 Jul 2;57(13):7568-7577. doi: 10.1021/acs.inorgchem.8b00364. Epub 2018 Jun 21.
Two coordination polymers (CPs), based on Cu(I)-I double zig-zag chains bearing isonicotinic acid or 3-chloroisonicotinic acid as terminal ligands with molecular recognition capabilities, have been synthesized and fully characterized. Both compounds present extended networks with supramolecular interactions directed by the formation of H-bonds between the complementary carboxylic groups, giving supramolecular sheets. The chloro substituent allows establishing additional Cl···Cl supramolecular interactions that reinforce the stability of the supramolecular sheets. These CPs are semiconductor materials; however, the presence of chlorine produces slight changes in the I-Cu-I chains, generating a worse overlap in the Cu-I orbitals, thus determining a decrease in its electrical conductivity value. These experimental results have also been corroborated by theoretical calculations using the study of the morphology of the density of states and 3D orbital isodensities, which determine that conductivity is mostly produced through the Cu-I skeleton and is less efficient in the case of the chloro derivative compound. A fast and efficient bottom-up approach based on the self-assembly of the initial building blocks and the low solutibility of these CPs has proved very useful for the production of nanostructures.
两种基于 Cu(I)-I 双锯齿链的配位聚合物（CPs），以异烟酸或 3-氯异烟酸作为末端配体，具有分子识别能力，已被合成并进行了全面表征。这两种化合物都具有扩展的网络，超分子相互作用是由互补羧酸基团之间形成氢键引导的，形成超分子片。氯取代基允许建立额外的 Cl···Cl 超分子相互作用，从而增强超分子片的稳定性。这些 CPs 是半导体材料；然而，氯的存在会对 I-Cu-I 链产生微小的影响，导致 Cu-I 轨道的重叠变差，从而降低其电导率值。这些实验结果也得到了理论计算的证实，使用了研究态密度和 3D 轨道等密度的形态，这确定了电导率主要是通过 Cu-I 骨架产生的，而在氯代衍生物化合物的情况下效率较低。基于初始构建块的自组装和这些 CPs 的低溶解度的快速高效的自下而上方法，对于生产纳米结构非常有用。
