TADF and X-ray Radioluminescence of New Cu(I) Halide Complexes: Different Halide Effects on These Processes.

A series of complexes [Cu2X2(Pic3PO)2] (X = Cl, Br, I) based on tris(pyridin-2-ylmethyl)phosphine oxide (Pic3PO) has been synthesized. At 298 K, these compounds exhibit thermally activated delayed fluorescence (TADF) of 1(M+X)LCT type with λmax varying from 485 to 545 nm, and quantum efficiency up to 54%. In the TADF process, the halide effect appears as the emission intensification and bathochromic shift of λmax in the following order X = I < Br < Cl. Upon X-ray irradiation, the title compounds emit radioluminescence, the emission bands of which have the same shape as those at TADF, thereby meaning a similar radiative excited state. By contrast to TADF, the halide effect in the radioluminescence is reversed: its intensity grows in the order X = Cl < Br < I, since heavier atoms absorb X-rays more efficiently. These findings essentially contribute to our knowledge about the halide effect in the photo- and radioluminescent Cu(I) halide emitters.

Synchronized Offset Stacking: A Concept for Growing Large-Domain and Highly Crystalline 2D Covalent Organic Frameworks.

Covalent organic frameworks (COFs), formed by reversible condensation of rigid organic building blocks, are crystalline and porous materials of great potential for catalysis and organic electronics. Particularly with a view of organic electronics, achieving a maximum degree of crystallinity and large domain sizes while allowing for a tightly π-stacked topology would be highly desirable. We present a design concept that uses the 3D geometry of the building blocks to generate a lattice of uniquely defined docking sites for the attachment of consecutive layers, thus allowing us to achieve a greatly improved degree of order within a given average number of attachment and detachment cycles during COF growth. Synchronization of the molecular geometry across several hundred nanometers promotes the growth of highly crystalline frameworks with unprecedented domain sizes. Spectroscopic data indicate considerable delocalization of excitations along the π-stacked columns and the feasibility of donor-acceptor excitations across the imine bonds. The frameworks developed in this study can serve as a blueprint for the design of a broad range of tailor-made 2D COFs with extended π-conjugated building blocks for applications in photocatalysis and optoelectronics.