An Open-shell, Luminescent, Two-Dimensional Coordination Polymer with a Honeycomb Lattice and Triangular Organic Radical

Abstract

The use of organic radicals as building blocks is an effective approach to the production of open-shell coordination polymers (CPs). Two-dimensional (2D) CPs with honeycomb spin-lattices have attracted attention because of the unique electronic structures and physical properties afforded by their structural topology. However, radical-based CPs with honeycomb spin-lattices tend to have low chemical stability or poor crystallinity, and thus novel systems with high crystallinity and persistence are in strong demand. In this study, a novel triangular organic radical possessing three pyridyl groups, tris(3,5-dichloro-4-pyridyl)methyl radical (trisPyM) was prepared. It exhibits luminescence, high photostability, and a coordination ability, allowing formation of defined and persistent 2D CPs. Optical measurements confirmed the luminescence of trisPyM both in solution and in the solid state, with emission wavelengths, λ_em, of 665 and 700 nm, respectively. trisPyM exhibits better chemical stability under photoirradiation than other luminescent radicals: the half-life of trisPyM in CH₂Cl₂ was 10 000 times that of the tris(2,4,6-trichlorophenyl)methyl radical (TTM), a conventional luminescent radical. Complexation between trisPyM and Zn^II(hfac)₂ yielded a single crystal of a 2D CP <b>trisZn</b>, possessing a honeycomb lattice with graphene-like spin topology. The coordination structure of <b>trisZn</b> is stable under evacuation at 60 °C. Moreover, <b>trisZn</b> exhibits luminescence at 79 K, with λ_em = 695 nm, and is a rare example of a luminescent material among 2D radical-based CPs. Our results indicate that trisPyM may be a promising building block in the construction of a new class of 2D honeycomb CPs with novel properties, including luminescence.