# Linker-Dependent Variation in the Photophysical Properties of Dinuclear 2-Phenylpyridinato(salicylaldiminato)platinum(II) Complexes Featuring NDI Units

## TL;DR

This study explores how flexible linkers affect the optical properties of a new type of platinum-based complex with potential for optoelectronic applications.

## Contribution

The paper introduces a flexible D-A-D complex with NDI units and demonstrates linker-dependent through-space charge transfer.

## Key findings

- Compound 1a (n = 3) adopts an S-shaped conformation, leading to a distinct TSCT absorption band.
- Linker length controls the spatial arrangement and photophysical behavior of the complex.
- DFT and experimental data confirm the folded conformation and TSCT behavior in flexible systems.

## Abstract

Through-space charge transfer (TSCT) between spatially adjacent donor and acceptor units has garnered considerable attention as a promising design principle for optoelectronic materials. While TSCT systems incorporating rigid spacers have been extensively studied to enhance through-space interactions, transition metal complexes connected by flexible linkers remain underexplored, despite increasing interest in their potential TSCT behavior. Herein, we report the design and synthesis of a donor–acceptor–donor (D-A-D)-type complex (1), in which a central naphthalenediimide (NDI) electron acceptor is linked to 2-phenylpyridinato(salicylaldiminato)platinum(II) complexes via flexible alkyl linkers. By systematically varying the linker length (n = 3, 4, 5, 6; 1a–d), we achieved precise control over the spatial arrangement between the NDI core and the platinum moieties in solution. Notably, compound 1a (n = 3) adopts an S-shaped conformation in solution, giving rise to a distinct TSCT absorption band. The structural and photophysical properties were thoroughly investigated using single-crystal X-ray diffraction, 1H NMR, NOESY analysis, and DFT calculations, which collectively support the existence of the folded conformation and associated TSCT behavior. These findings highlight that TSCT can be effectively induced in flexible molecular systems by exploiting intramolecular spatial proximity and non-covalent interactions, thereby offering new avenues for the design of responsive optoelectronic materials.