Cost efficient synthesis of bismuth aminoalkoxides from bismuth oxide: Molecular structure of [Bi2(mdea)2(mdeaH)2](mdeaH2)2

Photochemical solution processing of films of metastable phases for flexible devices: the β-Bi2O3 polymorph

“…1a). With the exception of the Bi – O(H) bond, these distances are in the range of those measured for the β-Bi 2 O 3 polymorph, with the bismuth in a pseudo-octahedral geometry841424344. Therefore, the transition from one to the other seems natural and can occur at very low temperature, as it happens here.…”

“…The molecular structure of the bismuth (III) – N -methyldiethanolamine coordination complex has been determined by single crystal X-ray diffraction8, indicating that bismuth atoms are surrounded by three short primary Bi – O bonds (2.150 Å), two transannular Bi – N bonds (2.729 Å, 2–746 Å) and two long Bi – O bonds corresponding to the association of the monomeric units into dimmers with asymmetrical Bi – O bridges (2.169 Å, 2.692 Å), as well as to the partially Bi – O(H) deprotonated diol (3.093 Å) (inset of Fig. 1a).…”

“…Additionally, CSD provides a particular advantage; the tailoring of the solution chemistry to achieve special processing targets (e.g., to reduce the high temperatures conventionally used, over 600 °C)123456. Recent developments in the preparation of metal oxide thin films by solution methods have made use of a specifically design of homo- and hetero-metallic molecular complexes aimed either at the reproduction of a molecular structure similar to that of the crystal structure of the oxide phase to be synthesized in the film, or at the increase of their photosensitivity for irradiation purposes27891011. Within the framework of the CSD methodology, sensitive metal coordination complexes have shown a huge potential for the processing of oxide thin films at low temperatures (<400 °C), like several Pb- and Bi-based ferroelectric perovskites1011.…”

A UV-absorber bismuth(iii)-N-methyldiethanolamine complex as a low-temperature precursor for bismuth-based oxide thin films

“…The chemical shis corresponding to carbons and protons belonging to mdea (C e , C f , C g and H g , H h , H i ) are recorded as multiplets in these spectra. These splitted signals, associated with sterically non-equivalent mdea groups, can be explained by the coordination of mdea to bismuth and the formation of a dimeric metal complex, as proposed by Le Bris et al 24 In addition, the NMR spectra reveal the existence of esters and di-esters in the Bi(III)-mdea sol, which result from the reaction between the solvents, acetic acid and 1,3-propanediol, during synthesis. This can be deduced from the higher intensity of the signal at $170.73 ppm, ascribed to the C b atoms of the ester/di-ester, compared to that at $175.20 ppm, due to the C b atoms of the acetic acid (Fig.…”

“…13, 16,24,28 The complex contains Bi(III), a d 10 element, where ligand eld excited states are not possible. Charge transfer (CT) transitions in this complex may occur from a molecular orbital with a predominantly metal-like (M) character to another one with a ligand-like (L) character, exhibiting photoreactivity promoted by MLCT transitions.…”