Methods of making metal-organic frameworks with pre-ligands

A method of making a metal-organic framework comprising:

• combining a first pre-ligand and at least one of a second pre-ligand or a first ligand, with a metal source comprising a metal component to provide a plurality of reactants;
• adding a solvent to the plurality of reactants to form a reaction mixture, wherein at least 50 wt. % of the reaction mixture is the plurality of reactants;
• heating the reaction mixture wherein the first pre-ligand is converted to a second ligand in the reaction mixture, the second pre-ligand if present is converted to a third ligand in the reaction mixture, and the second ligand and the at least one of the first ligand or third ligand react with the metal component;
• and
• cooling the reaction mixture to produce an insoluble portion and a soluble portion, wherein the insoluble portion comprises a plurality of the metal-organic frameworks, each metal-organic framework comprising at least one ligand and the metal component,
• wherein the first pre-ligand is selected from the group consisting of dimethylfumarate, dimethyl terephthalate, terephthalonitrile (1,4-dicyanobenzene), terephthalamide (1,4-benzenedicarboxamide), N1,N4-dimethylterepthalamide, dimethyl 2-aminoterephthalate, dimethyl 2-nitroterephthalate, dimethyl 2-chloroterephthalate, dimethyl 2-bromoterephthalate, trimethyl 1,2,4-benzene tricarboxylate, trimethyl 1,3,5-benzene tricarboxylate, tetramethyl 1,2,4,5-benzene tetracarboxylate, polyethylene terephthalate, and mixtures thereof,
• wherein the second pre-ligand is selected from the group consisting of C2-C10 linear or branched alkyl esters of fumarate, terephthalate, 2-aminoterephthalate, 2-nitroterephthalate, 2-chloroterephthalate, 2-bromoterephthalate, 1,2,4-benzene tricarboxylate, 1,3,5-benzene tricarboxylate, 1,2,4,5-benzene tetracarboxylate, and mixtures thereof, and
• wherein the first ligand is selected from the group consisting of fumaric acid, terephthalic acid, 2-aminoterephthalic acid, 2-nitroterephthalic acid, 2-chloroterephthalic acid, 2-bromoterephthalic acid, 1,2,4-benzene tricarboxylic acid, 1,3,5-benzene tricarboxylic acid, 1,2,4,5-benzene tetracarboxylic acid, and mixtures thereof.