Catalytic Synthesis of Donor-Acceptor-Donor (D-A-D) and Donor-Acceptor-Acceptor (D-A-A) Pyrimidine-Ferrocenes via Acceptorless Dehydrogenative Coupling: Synthesis, Structures, and Electronic Communication

Abstract

The synthesis and full characterization of a series of ferrocene-decorated pyrimidines with donor-acceptor-donor (D-A-D) and donor-acceptor-acceptor (D-A-A) architectures are reported. The three novel compounds share a pyrimidine core and single ferrocenyl donor arm, with an additional substituent varied from donor ferrocene (1) to acceptor pyrenyl (2) to donor (4-diphenylamino)­phenyl groups (3). The compounds could be easily constructed in acceptable yields in one-pot reactions via acceptorless dehydrogenative coupling reactions mediated by a ruthenium coordination complex supported by a simple bidentate P^N ligand. The solution and solid-state structures of the new pyrimidines are described along with photophysical and computational characterization. The lack of near IR (NIR) transitions upon single-electron oxidation of the compounds implies that the pyrimidinyl unit is less effective at mediating electronic communication compared with pyridine or pyrrole cores. Nevertheless, strong absorption in the far visible and NIR is observed upon formation of a dicationic species from 3 and is attributed to efficient charge transfer from the pyrimidine core to the oxidized donor units.

Tandem Hydrogen‐Borrowing Dehydrogenative Coupling and Hydrodefluorination

“…We previously established the utility of a ruthenium hydrido chloride complex ( [Ru] ; Figure 2) of a simple, bidentate P ^ N ligand bearing diphenylphosphine and phenanthridine (benzo[ c ]quinoline) donors in catalyzing ADC reactions to generate N ‐heterocycles such as pyridines, quinolines and pyrimidines, [29] including luminescent analogs [30] and near‐IR absorbing organometallics [31] from alcohols. In these reactions, elimination of H 2 under open reflux helps drive DC to high levels of completion (e. g., enabling isolated yields of >80% for tetrahydroquinolines).…”

Novel Ferrocenyl‐azole Derivatives: Synthesis, DFT Calculation and Unlocking the Anticancer Potential

“…Computational study is a significant method to generate optimal geometry, electronic structure, [37] and evaluate multiple characteristics of the molecular structure, [38] stability, [39] reactivity, [40] and biological activity. [41][42][43] The geometry of compound 4 ac and 5 ad were optimized in the gas phase using B3LYP/6-31G* level of theory, without using any symmetry constraint (Figure 2).…”

Photophysicochemical and electrochemical properties of pyrene–BODIPY platforms

“…[15][16][17] On the other hand, significant differences in the absorption and emission wavelengths result from altering the substitution pattern on the pyrrole moiety of the BODIPY core. [18][19][20] Additionally, a partial change in the maximum absorption wavelength was observed when it was substituted from the boron center. 21 Zatsikha et al prepared a new pyrene substituted BODIPY compound at the pyrrole unit and its weakly bonded noncovalent complexes with nanocarbon materials (single-walled carbon nanotubes (SWCNT), graphene, C 60 , and C 70 ).…”

“…15–17 On the other hand, significant differences in the absorption and emission wavelengths result from altering the substitution pattern on the pyrrole moiety of the BODIPY core. 18–20 Additionally, a partial change in the maximum absorption wavelength was observed when it was substituted from the boron center. 21…”