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Thus, in the present work, a new strategy for ligand design is reported, where piperazine and dihydrophenazine units are used as substitutes for benzene rings, which are the basic building block of most MOF ligands. This chemistry, which is based on simple, nucleophilic aromatic substitution (S\n                    <jats:sub>N<\/jats:sub>\n                    Ar) reactions, is used for the transition metal catalyst\u2010free construction of 21 new, carboxylate\u2010based ligands with varying sizes, shapes, and denticity and 15 linear di\u2010 and tetra\u2010nitriles. Moreover, to demonstrate the utility of the ligands as building blocks, 16 new structurally diverse MOFs having surface areas up to 3100\u2005m\n                    <jats:sup>2<\/jats:sup>\n                    \u2009g\n                    <jats:sup>\u22121<\/jats:sup>\n                    were also synthesized.\n                  <\/jats:p>","DOI":"10.1002\/anie.202215595","type":"journal-article","created":{"date-parts":[[2023,2,15]],"date-time":"2023-02-15T05:43:49Z","timestamp":1676439829000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":13,"title":["A Simple, Transition Metal Catalyst\u2010Free Method for the Design of Complex Organic Building Blocks Used to Construct Porous Metal\u2013Organic Frameworks"],"prefix":"10.1002","volume":"62","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-8013-5885","authenticated-orcid":false,"given":"Ilia","family":"Kochetygov","sequence":"first","affiliation":[{"name":"Institute of 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