RT info:eu-repo/semantics/article
T1 Columnar mesomorphism in molecular alloys based on Halogen-Bridged PtII/PtIV mixed valence complexes. The key role of the PtII/PtIV ratio
A1 Domingo de la Rubia, Estela de
A1 García Moreno, Gregorio José
A1 Coco Cea, Silverio
K1 Metallomesogens
K1 Triphenylene based liquid-crystals
K1 Mixed-Valence Complexes
K1 Molecullar Alloys
K1 Quantum chemical calculation
K1 23 Química
AB In this paper, we studied the thermotropic behavior and phase diagrams of blends of two platinum-based met-allomesogens with different oxidation states and ligands, which are prone to self-association through the for-mation of a mixed-valence system via PtII⋅⋅⋅Cl-PtIV interactions. The constituent molecules are cis-[PtCl2(CNL)2](CNL = 2-(6-(4-isocyanophenoxy)hexyloxy)-3,6,7,10,11-pentakisdodecyloxytriphenylene) and [PtCl4(Bipy)](Bipy = didodecyl 2,2′-bipyridyl-4,4′-dicarboxylate), which display an organic/inorganic segregated multi-columnar mesophase and a lamellar mesomorphism, respectively. Firstly, the phase diagram was constructedusing polarized optical microscopy, differential scanning calorimetry and X-ray scattering data. The resultsindicated that compositions exceeding 50 % of [PtCl2(CNL)2] led to columnar mesophases very similar to the oneof pure [PtCl2(CNL)2], where triphenylene cores and platinum moieties are segregated into different columnarunits. Then, employing tight-binding quantum chemical methods, we studied the supramolecular organization inthe columnar mesophases, as well as the electronic structure properties of mixtures with compositions larger than50 % of [PtCl2(CNL)2]. The results revealed that the formation of the metal–organic columns relies on a finebalance between PtII⋅⋅⋅PtII and PtII⋅⋅⋅Cl-PtIV intermolecular interactions, which strongly depend on the compo-sition of the system. A deep analysis of the density of states showed that lower concentrations of [PtCl4(Bipy)]result in a hole-doped system, while at higher [PtCl4(Bipy)] concentrations the intervalence charge transferbetween the metal center in different oxidation states significantly changes the electronic structure.
PB Elsevier
SN 0167-7322
YR 2025
FD 2025
LK https://uvadoc.uva.es/handle/10324/76152
UL https://uvadoc.uva.es/handle/10324/76152
LA eng
NO Journal of Molecular Liquids, 2025, vol. 431, p.127663
NO Producción Científica
DS UVaDOC
RD 26-jul-2025