Synthesis and characterization of Lindqvist-type polyoxometalate–porphyrin copolymers

Polyoxometalate-Based Photoactive Hybrid: Uncover the First Crystal Structure of Covalently Linked Hexavanadate-Porphyrin Molecule

“…Introducing metal sites with the suitable coordination capability to link metalloporphyrins with a carboxylic/pyridyl moiety has been an efficient strategy to obtain stable POM–metalloporphyrin organic frameworks (PMOFs). ,,, The covalent strategies may greatly improve the electronic communications between POM and porphyrins. − Owing to the pioneering research studies conducted by Kojima et al., , Ruhlmann et al, ,− and Zhou et al, ,, various covalently linked POM–porphyrin hybrids have been achieved. Representative strategies for those covalently linked POM–porphyrin hybrids include: (1) covalent attachment of a POM’s terminal oxo ligands to metalloporphyrins, or graft POMs’ pyridyl groups to the metal ions in metalloporphyrins, or graft pyridyl groups on porphyrin to POMs; (2) electropolymerization of POM-grafted pyridyl groups and metalloporphyrins, , and (3) direct tris-alkoxylation of POMs and tris-modified metalloporphyrins. ,,, Even though several covalently linked POM–porphyrin molecules have been reported before, previous POM–porphyrin interfaces have been focused mainly on Dawson-type POMs or Anderson-type POMs . To our knowledge, the direct tris-alkoxylation of Lindqvist-type POMs with tris-modified porphyrins has never been reported before.…”

“…44−47 Owing to the pioneering research studies conducted by Kojima et al, 47,48 al., 37,49−51 and Zhou et al, 46,52,53 various covalently linked POM−porphyrin hybrids have been achieved. Representative strategies for those covalently linked POM−porphyrin hybrids include: 54 (1) covalent attachment of a POM's terminal oxo ligands to metalloporphyrins, 47 or graft POMs' pyridyl groups to the metal ions in metalloporphyrins, 50 or graft pyridyl groups on porphyrin to POMs; 55 (2) electropolymerization of POM-grafted pyridyl groups and metalloporphyrins, 51,56 and…”

Synthesis and Characterization of Bisthienylethene‐Porphyrin Photoswitchable Copolymers

“…Scheme 1 presents the electropolymerization process. The principle of electropolymerization of zinc octaethyl porphyrin in the presence of pyridine containing spacers have been developed by our group and multiple examples have been published so far [27–29] . The process involves the formation of a porphyrin dication by raising the electrode potential to positive values (step V in Figure 1, above 1 V vs .…”

Recent advances in electrochemical meso- and β-functionalization of porphyrins and electrografting of diazonium porphyrins

“…Scheme 2. Functionalization of porphyrin monomers (A, [11,36,38,41,42]); preparation of oligomers (B, [37]); synthesis of copolymers (C, [43][44][45][46][47][48][49][50]).…”

“…Spectroelectrochemical studies on the material suggested the formation of π-dimers when the viologen moieties were reduced at the first reduction potential. Varying the POM and the porphyrin nature, the "easy" electrocopolymerization procedure was extended to Lindqvist-type polyoxovanadate (TBA2[V6O13{(OCH2)3CNHCO(4-C5H4N)}2] substituted with two pyridinyl groups and ZnOEP or 5,15-ditolyporphyrin free base [47]. It was shown by EQCM measurements that the electrocopolymerization was much more efficient with ZnOEP than with the disubstituted 5,15-ditolyporphyrin.…”