With the purpose to develop long chain-conjugated oligopyrrin-like compounds and their metal complexes, and thus achieve tunable near-infrared absorption, a dithienyl-blocked hexapyrrane ${\mathrm{\text{S}}}_2-{\mathrm{\text{P}}}_6$ was synthesized by acid-catalyzed [2+4+2] condensation, followed by oxidation with DDQ to afford dithiaoctapyrrin 1, and its mononuclear metal complexes 1-Cu and 1-Zn were synthesized by treating 1 with Cu(II) and Zn(II) acetates. All the compounds were systematically characterized by NMR/EPR, and HRMS. The crystal structures revealed that 1 adopts a double hook-like conformation. Whereas, both complexes 1-Cu and 1-Zn adopt spiral-hook hybrid conformations, showing smaller interplanar angles between the rings within the spiral part, compared with those in the hook-like counterpart of molecule 1, which is favorable for red-shifting the absorption. As expected, the absorption band edges for complexes 1-Cu and 1-Zn are red-shifted to ca. 1560 nm, compared with that of 1260 nm observed for 1.

为了开发长链共轭低聚吡啶类化合物及其金属配合物，从而实现可调谐的近红外吸收，一种二噻吩基封闭的六吡喃${\mathrm{\text{S}}}_2-{\mathrm{\text{磷}}}_6$通过酸催化[2+4+2]缩合，然后用DDQ氧化得到二硫代八吡林1，并用Cu(II)和Zn处理1合成了其单核金属配合物1-Cu和1- Zn( II) 醋酸盐。所有化合物均通过 NMR/EPR 和 HRMS 进行了系统表征。晶体结构显示1采用双钩状构象。而配合物1-Cu和1-Zn均采用螺旋钩杂化构象，与分子1的钩状对应物相比，螺旋部分内环之间的面间角更小，这有利于吸收的红移。正如预期的那样，配合物1-Cu和1-Zn的吸收带边缘红移至约。1560 nm，与1观察到的 1260 nm 相比。