Theoretical Chemistry Accounts

, 134:150 | Cite as

Negative solvatochromism of push–pull biphenyl compounds: a theoretical study

  • Suci Meng
  • Stefano Caprasecca
  • Ciro Achille Guido
  • Sandro Jurinovich
  • Benedetta Mennucci
Regular Article

Abstract

We have investigated the negative solvatochromism observed for 4-(phenyloxido)-N-methylpyridinium in solvents of varying polarity using a hierarchy of solvation models (continuum, discrete, and mixed) combined with a (TD)DFT description. Overall, the significant hypsochromic shift measured in the experiments is reproduced qualitatively and quantitatively through calculations. More in detail, the role played by the solvent in tuning the spectral properties of POMP has been correlated with geometrical and electronic effects, and the ππ aggregation effects of POMP have been shown to be important in solvents of low and medium polarity.

Keywords

Hypsochromic shift Zwitterionic compounds Solvation model TD-DFT Molecular dynamics QM/MM 

Supplementary material

214_2015_1754_MOESM1_ESM.pdf (354 kb)
Optimized geometries of POMP in CCl4, CHCl3, CH2Cl2, (CH3)2CO, DMSO, and H2O using PCM method at the B3LYP/6-31+G** level (Table S1); optimized geometries of isolated POMP and the supermolecular clusters with 1–4 water molecules in aqueous solution within the PCM framework using B3LYP/6-31+G** (Table S2); evolution of the interaction potentials of POMP–H2O and H2O–H2O dimers as a function of the intermolecular distance, r. The data are obtained from MP2/6-31+G**, B3LYP/6-31+G**, M06-2X/6-31+G** calculations, and PCFF results with PCFF, ESP, NBO, as well as Mulliken partial charges, respectively (Figure S1); the geometrical structures and excitation energies of supermolecule clusters with different size (Figure S2); RDFs for oxygen atoms in POMP to hydrogen atoms in DMSO solution and probability distributions of CH–O angle of POMP in DMSO solution within the first solvation shell (Figure S3); radial distribution functions for oxygen atoms in POMP dimer to hydrogen atom in acetone solution and probability distributions of O–H–C angle of POMP dimer in acetone solution within the first solvation shell (Figure S4); probability distributions of solvent coordination number and three-dimensional probability distributions of solvent molecules involving CH–O hydrogen bonding interactions of O1 and O2 atoms of dimeric POMPs in acetone solution within the first solvation shell (Figure S5) (PDF 353 kb)

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Copyright information

© Springer-Verlag Berlin Heidelberg 2015

Authors and Affiliations

  • Suci Meng
    • 1
    • 2
  • Stefano Caprasecca
    • 3
  • Ciro Achille Guido
    • 3
  • Sandro Jurinovich
    • 3
  • Benedetta Mennucci
    • 3
  1. 1.School of Chemistry and Chemical EngineeringJiangsu UniversityZhenjiangPeople’s Republic of China
  2. 2.Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical EngineeringNanjing UniversityNanjingPeople’s Republic of China
  3. 3.Department of ChemistryUniversity of PisaPisaItaly

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