Nanopore-induced host–guest charge transfer phenomena in a metal–organic framework

A spontaneous entrapment of electron-donating small guest molecules, including tetrathiafulvalene (TTF) and N,N,N′,N′-tetramethyl-1,3-propanediamine (TMPDA), was realized in a structurally flexible metal–organic framework, {Mn(7)(2,7-AQDC)(6)(2,6-AQDC)(DMA)(6)}(∞) (AQDC = anthraquinone dicarboxylates, DMA = N,N-dimethylacetamide), with electron-accepting anthraquinone groups, generating two MOF guest charge transfer complexes: {Mn(7)(2,7-AQDC)(6)(2,6-AQDC)(DMA)(6)(TTF)(5)} and {Mn(7)(2,7-AQDC)(6)(2,6-AQDC)(DMA)(4)(H(2)O)(2)(TMPDA)(7)}. Using a mild impregnation procedure, single crystals of the target complexes were obtained via a crystal-to-crystal conversion, and the crystals were suitable for structural analysis. Single crystal X-ray analysis demonstrated the different arrangements of these intercalated donor molecules: some donor molecules interacted with the anthraquinone groups and formed infinite D–A–A–D stacks, some appeared beside the anthraquinone groups but only formed donor–acceptor pairs, and the remainder of the molecules simply filled the space. The charge transfer between the guests and the framework was spectroscopically confirmed, and the radical densities on the organic species were estimated using magnetic susceptibility measurements. Compared with a solid-state mixture of anthraquinone and donor molecules, the evenly distributed donor molecules in the micropores of the MOF resulted in a “solid solution” state and significantly promoted the degree of charge transfer between donors and acceptors. Such an encapsulation process may be adopted as a new strategy for post-modification of the electronic and magnetic properties of MOFs, as well as for generating new semiconducting charge-transfer complexes.