Facilitating Charge Transfer via Ti–Knot Pathway in Electrochromic Three-Dimensional Metalated Covalent Organic Frameworks

Due to the ordered one-dimensional channel as well as accessible redox sites, two-dimensional covalent organic frameworks (2D COFs) have garnered extensive attention in the field of electrochromism. However, organic 2D frameworks impose limitations on charge transfer and the weak interlayer interactions in 2D COFs, adversely affecting the stability during switching processes. Herein, we introduced Ti knots to construct three-dimensional metalated covalent organic frameworks (3D MCOFs), denoted as Ti-DHTA-Py. The Ti knots not only serve as templates for organizing organic units into unique 3D topological structures in a controlled manner but also establish charge transfer pathways conducive to electron delocalization and transmission within the framework. As a result, the 3D Ti-DHTA-Py MCOFs electrode exhibited a reduced band gap and remarkable electrochromic (EC) performances: electrochemical cyclic stability of 93.6% retention after 500 cycles, switching times (2.5 s/0.5 s), and a high coloration efficiency (423 cm 2 C –1 ). This research underscores the potential of 3D MCOFs as promising candidates for advancing EC technologies, surmounting the limitations associated with traditional 2D COFs.