Novel s‐Block Metal Pyridinedicarboxylate Network Structures through Gas‐Phase Thin‐Film Synthesis

: The combined atomic and molecular layer deposition (ALD/MLD) technique offers a unique way to build-both known and previously unknown-crystalline coordination polymer materials directly from gaseous precursors in a high-quality thin-film form. Here, we demonstrate the ALD/MLD of crystalline Li-, Na-, and K-based 3,5-pyridinedicarboxylate (3,5-PDC) thin films; the Li2 -3,5-PDC films are of the known Li-ULMOF-4 crystal structure whereas the other as-deposited crystalline films possess structures not previously reported. Another exciting possibility offered by ALD/MLD is the deposition of well-defined but amorphous metal-organic thin films, such as our Mg-, Ca-, Sr-, and Ba-based 3,5-PDC films, which can then be crystallized into water-containing structures through a post-deposition humidity treatment. All together, the new metal-organic structures realized in this study through ALD/MLD comprise a majority of the (anhydrous and water-containing) members of the s-block metal 3,5-pyridinedicarboxylate family.