A Fused Poly(truncated rhombic dodecahedron)-Containing 3D Coordination Polymer: A Multifunctional Material with...

The design of new and inexpensive metal-containing functional materials is of great interest. Herein is reported a unique thermochromic near-IR emitting coordination polymer, 3D-[Cu₈I₈(L1)₂], CP2, which is formed when ArS(CH₂)₄SAr (L1, Ar = 4-C₆H₄OMe) reacts with 2 equiv of CuI in EtCN. In MeCN, CP1 ([Cu₄I₄(L1)(MeCN)₂], consisting of an alternating [-Cu₄I₄-L1-Cu₄I₄-L1-] chain where the Cu₄I₄ cubane units bear two metal-bound MeCN molecules, is formed. Heat-driven elimination of these MeCN's in solid CP1 also leads to CP2 through a predisposed organization of the Cu₄I₄ units prone to fusion after MeCN eliminations (i.e., a rare case of template effect). The CP2 structure exhibits parallel 1D-(Cu₈I₈) chains, (z-axis; designated 1D-[CuI]) as secondary building units (SBU) held together by parallel thioether ligands (x,y-axes), forming a nonporous 3D network. The structure of this 1D-[CuI] SBU is unprecedented and consists of a series of fused and twisted open Cu₄I₄ cubanes forming a fused poly(truncated rhombic dodecahedron). Unexpectedly, the compact 3D CP2 exhibits a solid-to-solid phase transition at 100 °C and a hysteresis of ∼20 °C. CP1 emits intensively (298 K: λ_emi = 564 nm; Φ_e = 0.35), whereas CP2 presents a strongly red-shifted weaker emission (298 K: λ_emi ∼ 740 nm, Φ_e < 0.0001). Moreover, CP2, which is stable over long periods of time, exhibits thermochromism where the emission intensity of the near-IR band decreases significantly at the benefit of a ligand-centered phosphorescence at 415 nm. Altogether, these properties listed above make CP2 exceptional. The low-energy singlet and triplet excited states have been assigned to ligand/metal-to-ligand charge transfer based on DFT and TD-DFT computations.