Al3+ induced planarization, conformational arrest and metallochromic shift in a pyrimidine dione dye: insight from integrated hybrid quantum-classical calculations
2012 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 14, no 7, 2339-2345 p.Article in journal (Refereed) Published
In order to explore the possibilities of simulating metallochromism by modern molecular modeling, we apply a sequential hybrid quantum-classical approach to a prototype metallochromic system-the Al3+ ion and pyrimidinedione (PY) dye complex. The complex shows several structural features with relevance for the metallochromism: the PY dye exhibits conformers with dynamical transitions between twisted structures, which are inhibited by the addition of the metal ion leading to planarization and a conformational arrest: the Al3+ ion behaves like a structure-modifier for both intra and intermolecular degrees of freedom and with respect to the intermolecular solvation shell structure. The sequential approach that we have employed uses DFT/MM molecular dynamics for structure modeling and TDDFT/PCM for property modeling. The computed metallochromic shift between PY and the Al(PY)(3+) complex in DMSO solvent is obtained in excellent agreement with experiment. The results infer optimism for future use of such modeling techniques to design metallochromic indicators.
Place, publisher, year, edition, pages
2012. Vol. 14, no 7, 2339-2345 p.
IdentifiersURN: urn:nbn:se:kth:diva-90666DOI: 10.1039/c2cp23238cISI: 000299505400028ScopusID: 2-s2.0-84856731246OAI: oai:DiVA.org:kth-90666DiVA: diva2:506193
FunderSwedish e‐Science Research Center
QC 201202282012-02-282012-02-272013-04-08Bibliographically approved